Compositions comprising an organic polymer and an organo phosphorus compound



nite Staes assiguor to Monsanto a corporation of The present inventionrelates to improved organic materials, and more particularly deals withhighly polymeric substances such as are employed in the manufacture ofmolding and extruding compositions, films, sheets, fibers, textiles,papers, surfacing or coating compositions, impregnating agents, solidfoams, rubbers, etc. The invention provides compositions comprising suchpolymeric substances in combination with an adjuvant therefor which hasthe ability to modify in a favorable way the properties of the polymer.

Numerous adjuvants for use Wtih natural and synthetic highly polymericmaterials are known in the art, and in most instances such adjuvants arecapable only of modifying one property of a polymer or of a narrow classof polymers. Thus, while numerous compounds are known to plasticize aclass of vinyl polymers such as the vinyl chloride polymers, the samecompounds generally do not stabilize these polymers against heat and/ orlight, not do the same compounds possess plasticizing effect on anothertype of vinyl polymer such as polymethacrylates. Also, while a few knownadjuvants possess a broad spec trum of efficiency with respect to oneclass of polymers, say the phenolic resins generally, the same adjuvantspossess no efficiency when employed with other classes of polymers,e.g., the polyurethanes, the alkyds, or the cellulose esters. Thus,While one compound is known to be a very good flame-retardant for apolymer and is compatible therewith, the same compound, though it maystill confer flame-retardant effect, cannot be used with another polymerowing to incompatibility.

According to the present invention, it has been discovered that theclass of organic phosphorus compounds hereinafter disclosed possess theproperty of efiiciently modifying polymeric substances, generally, andthat members of this class of phosphorus compounds have the property offavorably afiecting more than one characteristic of the polymers.Natural and synthetic polymers, Whether linear or cross-linked, aremodified by adding the presently useful phosphorus compounds either tothe finished polymers or at any stage of the polymerization orcondensation process by which the polymers are prepared. The presentphosphorus compounds are also advantageously incorporated into thepolymers by adding them to the mixtures of monomer reactants to beemployed in the polymerization or condensation process and thenconducting the reaction.

The invention finds, perhaps, its greatest utility as a flame-retardantfor polymeric materials. Thus, as will be hereinafter disclosed, such adiversity of polymeric substances as paper, cotton cloth, the celluloseesters and ethers, polyvinyl chloride, polymethyl methacrylate, phenolaldehyde resins, the polyurethanes, alkyd resins, urea resins, thepolycarboxamides of the nylon type, polyacrylonitrile, the linear andcross-linked polyesters, maleic anhydride heteropolymers,styrene-methacrylate copolymers, polymerized olefins and diolefins, arerendered flame-retardant by the present phosphorus compounds. At thesame time, depending upon the quantity of the phosphorus compound whichis in contact with the polymer, plasticizing or softening eiiect isobtained. Thus, at'say, a to 50% concentration of the phosphoruscompound, based on the total of polymer and phosphorus compound, thepolymer generally not only is flame-proofed but also plasticized. Use ofthe present phosphorus compounds at much lower concentrations, say in anamount which in some cases is as low as 0.01% imparts a degree ofthermal stability, though better results are generally obtained by usinggreater amounts for this purpose, say quantities which are about 46% orupwards. The present phosphorus compounds may be used with the polymersin a quantity which is equal to that of the polymer, but in mostinstances favorable results with respect to improvement in heatstability and/ or flame retardance and/or plasticity is obtained atconcentrations which are definitely lower. It will be evident, ofcourse, that for the preparation of plastisols, quantities of thephosphorus compound which are greater than that of the polymer will berequired. Use of the present phosphorus compounds with the polymericmaterials in quantities which confer beneficial properties to thepolymers with respect to a desired effect, e.g., flexibility in the caseof a film, flame-proofing in the case of a foam insulator or thermalstability in the case of extruded fibers or molded pieces, often confersto the polymer an improvement also in such characteristics as resistanceto impact, dimensional stability, resistance to scorch in curing,moldability, etc. These varied effects are readily determinable by thoseskilled in'the art simply by visual observation or by use ofconventional techniques. Hence in order to arrive at optimum beneficialeffect suited to the purposes for which the polymeric composition isdesigned, only routine testing, involving variation of adjuvantquantity, is generally required, although in some instances one or moremembers of the whole class of the presently useful phosphorus compoundswill be found to impart a degree of modification at a low concentrationwhich can be attained by other members of the class at significantlyhigher concentrations.

The class of phosphorus compounds which is presently employed with thepolymers is characterized particularly by containing 2 or morephosphorus atoms, one of which may be trivalent andat least one of whichis bonded to carbon. Although individual members of the Whole class willdifier from each other in some respects, members of the class generallyare desirable adjuvants for high molecular weight polymeric materials.This may be ascribed to the recurrency of the 0-1 and O-P linkages whichis characteristic of the class; however, I cannot, at this time, makeclaim to any relationship between such structure and effect, nor can Iexplain the surprisingly broad spectrum of polymeric materials which arebeneficially modified by the presently useful compounds.

My invention consists only in the provision of an organic materialcomprising a polymer selected from the class consisting of natural andsynthetic, linear and crosslinked polymers in contact with not more thanan equal amount, based on the weight of the polymer, of an adjuvantwhich is an organic compound of the formula 0 O iooflliocfilhs I l Ll ll l where n is a number of 0 to 2, m is a number of 0 to when n is 2 and0 when n is less than 2, Y is selected from the class consisting of =P,EP=O, EP=S, each R is selected from the class consisting of hydrocarbyl,halohydrocarbyl, alkoxyhydrocarbyl, and (hydrocarbyloxy)halohydrocarbylradicals of from 1 to 12 carbon atoms and such radicals linked to thephosphorus atoms of Y by an element selected from the class consistingof -O-, and -S and wherein two Rs taken together stand for a radicalselected from the class -O-hydrocarbylene-O- and--O-halohydrocarbylene-O- radicals which are free of aliphaticunsaturation and which con- RnY halide such as phenyl 7 not has theformula :phosphorus atoms by treatment g i V 'tain from 2 to carbonatoms; R'" is selected from the class consisting of hydrocarbyl,halohydrocarbyl, alkoxyhalohydrocarbyl and hydrocarbyloxyhalohydrocarbylradicals'of' from 1 to 12 carbon atoms and such radicals linked to thephosphorus atoms by an element selected from the class consisting of Oand S; Z is selected from the class consistingof hydrogen, hydrocarbyl,halohydrocarbyl, carboalkoxyhydrocarbyl, alkylthiohydrocarbyl,alkoxyhydrocarbyl, and cyanohydrocarbyl radicals of from 1 to 17 carbonatoms when n is 2 and from 1' to 10 carbon atoms when nis less than 2,and the furyl and thienyl radicals; and R and Rf are selected from theclass'c'onsisting of alkyl, haloalkyl, aryl, haloaryl, alkoxy,haloalkoxy, and (hydrocarbyloxy)haloallgoxy radicals of from l to 12carbon atoms. 1

Some of the presently useful phosphorus compounds may be prepared by thereaction of a trivalent phosphorus compound having a halogen atom linkedto the phos phorus atom thereof, a carbonyl compound and an ester of atrivalent phosphorus acid, substantially described in my copendingapplication, Serial No. 780,209, filed December 15, 1958, now abandoned,and in thecontinuationin-part thereof, application Serial No.27,505,,filed May 9, 1960, which has issued as Patent No. 3,014,944.This reaction proceeds as follows;

G-u) (3I1)ZCHO (3 I V R, Y

are as 'herein' defined,

'RnP

where R, R and R, Z and 'n is selected from the class consistingofchlorine and brohaloalkyl and (hydrocarbyloxy)haloalkyl radicals offrom 1 to 12 carbon atoms;

The above reaction takes place by using substantially the number ofmoles of'the aldehyde ZCHOtand of the trivalent phosphorus ester R'R"POTwhich is substantial- 1y equal to the number of halogen atoms presentincthe phosphorus-halogen compound R PX the product has the formula L II Z R 3 Thus, if the phosphorus-halogen compound is phosphorustrichloride,

RV OCHP,R

When the phosphorus-halogen compound is, say, a diphosphorodichloridite,the product has the formula V ll' ZR 2,

When the phosphorus halogen compound is a monohalide Sac a2-chloro-1,3,2-dioxaphospholane, the prodoHi-o fir 'POCHPR" a It Willbenoted that all of the above compounds contain a trivalent'phosphorusatom. 'HoWever, they may be readily converted to compounds having onlypentavalent orthionating agent, substantially as describedin my ap-846,817, filed oer; 16,1959; Serial No. 847,684, filed Oct. 21, 1959;Serial No. 852,160, filed Nov. 12, 19,59; and

Serial No. 852,206, 'filed Nov. 12', 1959.

7 theme:

With either an oxodizing r the number ofmoles of an aldehyde and a trThe above compounds are thus converted to V V H V V(ClCHzOHzOXPOCHP(OCH2CH3)3 u if CICHZCHZP O CHI (0 CHzOHah CICHzCHgO HaHeat isomerizatiori of thesproducts obtained from a haloalkylphosphonohalidite, an aldehyde, and a trivalent phosphorus esterproceeds, e. g., .as follows:

V 06115110 onl n' OUE5i OGHi R" 'CH OHC1Gl1 0 z R 0112 01 HZ R I 7 s mMy application Serial No. 828,464, filed July 21,1959, which has issuedas Patent No. 3,014,956, describes preparation of thepentavalentphosphorus compounds by heat isomerization of the haloalkyltrivalent phosphorus esters which takes place substantially'according tothe V Xalk-OP,OCH1 R rear-i ooni nm VIIZZR I tZ'R"" here X is chlorineor bromine and R, R','R" and Z are as defined above. 7 l i I It willthus 'be evident that numerous compounds having one trivalent phosphorusatom and-from onetto three pentavalent phosphorushatoms are obtainedbyreacting together a trivalent phosphorus-halogen compound 'With ivalentphosphorus ester which are equal'to the number of halogen atoms presentin the phosphorus-halogen reactant; that where R, R, R", Z, Y and n areas defined above. And they are all prepared by intially starting with aquantity of the aldehyde and a quantity of the trivalent phosphorusester which are substantially equal to the number of halogen atomspresent in the phosphorus-halogen compound. The treatment with oxygen orsulfur or the heat treatment are subsequent steps which effect only aportion of the initial molecule, i.e., that which is derived from thephosphorus-halogen compound. Such subsequent treatment providescompounds having improved thermal stability and very good resistance tohydrolysis by water. Hence, for some purposes, those of the compoundswhich contain phosphorus only in the pentavalent form are particularlyuseful adjuvants for natural and synthetic fibers.

Some of the initial products, i.e., those containing one trivalentphosphorus atom present as a part of an alkyl or haloalkyl phosphite orphosphonite structure can be converted to still other compounds ofpresent utility. Such initial products, esters of a trivalent phosphorusacid, can react with additional quantities of a mono-halogen phosphoruscompound and of an aldehyde; thus when T is an alkyl or haloalkylradical and R, R, and R' are as herein defined the following occurs:

I! H m x ZOHO TOPOCHPOOHPR" R RUIZ RUIZ R! l RIEOCHl OCHl OCHI 'R R zR'Z RZ R The compound IV obviously has the formula 0 O [u l uRPiO(\3HO(lJH-IR R Z LR Z .Lrv

where n is 2. Compd. (III) has the same structure, with n being 1; andin the initial product, i.e., (I), n is zero. Of course, the furtherreaction of IV will depend upon whether the trivalent phosphorus atom isattached .to at least one alkoxy or haloalkoxy radical, since such aradical is required for reaction with a further quantity of phosphorushalogen compound and aldehyde. Bearing this in mind, compounds of thestructure (V) wherein n has an increasingly greater value are obtainedby prolonged addition of phosphorus halogen compound and aldehyde tointermediately formed products. Reaction ceases when the requiredquantities of aldehyde and halogen compound are no longer available orwhenever there is formed as product a compound which does not possessthe required phosphite (TO) PO- or phosphonite TOP(R)O- structure.

A very convenient method of preparing compounds having the structure V,where n is at least one is described in my copending application SerialNo. 820,618, filed June 16, 1959, which has issued as Patent No. 3,014,-954. According to this method, the ratio of trivalent phosphorus ester,aldehyde andtrivalent phosphorus halogen compound which are reactedtogether is such that the aldehyde and halogen compound are present insubstantially equimolar proportions and the trivalent phosphorus esteris present in less than an equimolar proportion with respect to theother two reactants. With such a ratio, using as the phosphorus halogencompound an ester of either phosphorochloridic acid or an ester ofphosphonochloridic acid, there is first formed the 1:1:1 product:

[I 'roroonrn" R z R! where T is an .alkyl or haloalkyl radical of 1-12carbon atoms. Formation :of the 121:1 product uses up the originallypresent trivalent phosphorus ester; and the excess of aldehyde andphosphorus halogen compound reacts with the newly formed trivalentphosphorus ester, i.e., the 1:1:1 product to give products of theformula 0 0 TOPOCH[-i"OCHj\-l R" 1'. r it ,i

where n is at least 1. The value of n is a function of the quantity ofphosphorus halogen compound and of the aldehyde which is available forreaction of intermediately formed products.

A commercially attractive process for preparing mixtures consisting ofphosphorus halogen compound and trivalent phosphorus ester, whichmixtures can then be reacted with an aldehyde to give the presentlyuseful products, comprises reaction of an oxirane compound withphosphorus trichloride or phosphorus tribromide in certain proportionsas disclosed in my copending application, Serial No. 780,262, filedDecember 15, 1958, which has issued as Patent No. 3,014,951. Thereaction of 5 moles of an oxirane compound, e.g., an alkylene oxide or aglycidyl ether, with 2 moles of a phosphorus halide results in theproduction of an equimolar mixture of phosphorohalidite and phosphite,e.g., with ethylene oxide as the oxirane compound and phosphorustrichloride there is obtained an equimolar mixture of bis(2-chloroethyl)phosphorochloridite and tris(chloroethyl) phosphite. When the oxiranecompound is a glycidyl other, there is obtained an equimolar mixture ofa bis(hydrocarbyloxyhalopropyl) phosphorohalidite andtris(hydrocarbyloxyhalopropyl) phosphite; e.g., from phenyl glycidylether and phosphorus tribromide in a 5:2 ratio there is obtained anequimolar mixture bis(3- henoxy 2 bromopropyl) phosphorobromidite andtris(3-phenoxy-2bromopropyl) V 7 ing product is obtained:

are then reacted with an aldeof the formula phosphite; Such mixtureshyde to give compounds where Y is selected from the class consisting ofhaloalkyl and'hydrocarbyloxyhaloalkyl radicals of from 2 to 12 carbonatoms. 7

However, when 2 moles of the phosphorus halide is reacted with lessthairS but more than 4 molesof the oxirane compound thephosphorohalidite and the phosphite are not formed in equimolarproportion; instead, the phosphorohalidite is in excess. tThusrwith 4.8moles of ethylene oxide and 2 moles of phosphorus trichloride there areobtainedLS moles of bis(2-chloroethyl) phosphorochloridite, and withonly 4.09 moles of the oxide' per molerof the tn'chloride there areobtained 21 moles of the phosphorochloridite per moleof the phosphite.As disclosed in my copending application Serial No. 820,618,

filed December 16, 1958, which has issued as Patent No.

prepared by reaction of 2 moles of phosphorus trichlo-' ride ortribromide with less than 5 moles but more than 4 moles of an oxiranecompound are particularlyuseful for preparing those of the presentlyuseful compounds which have a'plurality of the units RIIIZ Here theexcess of phosphorohalidite with respect tol phosphite which is requiredto produce compounds of this type is conveniently present. Thus when theratio of phosphorohalidite to phosphite is 21:1, the addition ofaldehyde in a quantity which is equimolar with respect to the haliditeresults in the production of a product having an average of such units,e.g., from ethylene om'de, phosphorus trichloride and propionaldehyde,the follow- (Cromcmohroon'iho H :li oomcrno1):

7 z 0 0 112011201 ,1; Wheren has an average .valueof 20. Because thereaction of each intermediately formed product with the excess ofphosphorochloridite and aldehyde proceeds very rapidly, the productobtained is a'mixture having vary- Hence the value given above, asceringvalues for n.

*tained by the quantity of reactants consumed and by 3,014,954, mixturesof phosphorohalidite and phosphite elemental analysis, is necessarily anaverage value. Ac- 7 a tually, the product probably'consists of mixturesin which n will vary from, say, Oto as high as 50, with the averagebeingZO. a t 1' Compounds containing a plurality of the units V p t v i7 it i phosphorus present-only'in the pentacan be oxidized, thionated,or heat isomerized to give products having -valent form. Upon reactionwith oxygen or sulfur the trivalent phosphorus atom is renderedpentavalent and the 7 products have the formula neroorr-roo t y t r l. RWhere E is oxygen or sulfur.

'The more simple ofthe present compounds, i.e., those 7 prepared from anequimolar mixture of a diester'offphosr phorochloridous acid, analdehyde, and a tribasicphos:

phite can be n amed as phosphites of l-hydroxyalkylis obtained by thereaction Vlarly in the reaction valent phosphorus ester,

8 phosphonate. Thusthe 1:1:1 react-ion product of bis(2 -chloroethyl).phosphorochloridite, butyraldehyde and tris(Z-chloroethyl) phosphite,said reaction product havingthe-structure r (ClCH2CHzO)zP O OHLIEI (OCEBU/H201):

V omomom can be named the his (2-'ch1oroethyl) phosphite of bis(2-chloroethyl) 1-hydroxybutylphosphonate. However, the more complexcompounds are more difficultly named and, accordingly, it is believedthat understanding of the invention will be best facilitated by simplypresenting the structural formula of each compound as reference to it isnecessary.

In the simple 1:1:1 reaction product R-P-O-OH-I R" R t it that portionwhich is derived from the mono-halo phosphorus compound is 7 t a VThatportion which is'derived from the aldehyde is -o orr and thatportion which is derived from the tribasic trivalent phosphorus ester isHence it will be'readily evident that a compound of the formula GHZ-O 7O PO CHP(OCHa)2 CH2O phenyl is obtained by the reaction of equimolarquantities of -2-halo-1,3,2-dioxaphosph0lane, i.e.,

'is derived from the mono-halo phosphorus compound,

9 is derived from the aldehyde, the portion is derived from the samemono-halo phosphorus compound and the same aldehyde and the portion ll]i) RII R! is derived from the tribasic phosphorus ester. Hence theproduct where n is at least 1 is obviously obtained from one mole of thephosphorus-halogen compound (CH CH O) PX, where X is chlorine orbromine, one mole of formaldehyde and less than one mole of trimethylphosphite.

When there are two replaceable halogens in the phosphorus halogencompound, and there are employed with 1 mole of such compound 2 moles ofthe aldehyde and two moles of the tribasic trivalent phosphorus ester,the product has the formula Here the portion R-P= is derived thephosphorus dihalide, RPX where X is chlorine and bromine and, as in theinstances above, the portion and R! are derived from the aldehyde andthe tribasic trivalent phosphite, respectively.

The product obtained from one mole of a phosphorushalogen compoundcontaining three replaceable halogen atoms and three moles each of thealdehyde and of the tribasic trivalent phosphorus 'ester has the formulai i P.OOHP-R" Z R a Here the compound was obviously derived from PXwhere X is chlorine or bromine, i.e., phosphorus trichloride orphosphorus tribromide or a mixed phosphorus trihalide having bothchlorine and bromine. The portions O (FH z and o I z and s o niooni n" RZ R are derived by oxidation or thionation of the compounds II R P 0 GHPR" R z R and compounds of the formula L at where n is at least 1 arederived by oxidation or thionation of the compounds As disclosed above,compounds in which all of the phosphorus is pentavalent are alsoobtained by heat rearrangement of a product in which at least one R ofthe portion is a haloalkoxy radical. Hence the compounds 0 0 r n l Z LR;R where n is a number of 0 to are obtained either by the oxidation of 0i H 1 ll haloalkyl-P 0 (IJHP 0 CHP B" it 2 LR Z R or by the heatrearrangement of Those of the products which have been obtained byreplacement of 2 or 3 halogen atoms of the phosphorus halogen compound,i.e., products of the formula also undergo oxidation or thionation.Hence the compound of the formula i u pheny1P O CH? (O CHa) 2 isobviously obtained by thionation of the reaction product of one mole ofphenyl phosphonous dichloride or dibromide with two moles each ofacetaldehyde and trimethyl phosphite. And the compound of the formula POOH? (0 01111011010113):

phenyl a is obviously obtained by oxidation of the'product obtained byreacting one mole of phosphorus trichloride or tribromide with threemoles each of benzaldehyde and ease with which the starting materialscan be ascertained by inspection of the structural formula as summarizedabove. The methods briefly asfollows:

The three reactants, i.e., thephosphorus halogen compound, the aldehydeand the tribasic trivalent phosphorus ester are mixed together in theproportions referred to above, either at ordinary, decreased orincreased temperatures; Because, generally, an exothermic reactionoccurs, it is usually advisable to contact the reactants with each otherin the cold and then to apply heat only if no reaction is evidencedafter all three reactants are mixed. After'reaction has ceased, whichcan be noted by lack of change in temperature or in viscosity, the

by-product halide and possibly any ,unreacted, original material isremoved, e.g.,' by distillation or extraction.

Depending upon the proportion of reactants employed,

the residue is the substantially pure product; of the structure a u r nV ,RnP 0QH POCHPR" g V RHIZ L l al v where n is a number, of Oto 2, 'mis a number of O to 100 when n is 2 and 0 when n-is less than 2, and R,Z, R and R" are as hereinbefore defined. All of such compoundslcan beoxidized by treatment with an oxidizing agent such as oxygen, ozone,hydrogen peroxide, a hydroperoxide, a nitrogen oxide, or a percarboxylicacid at ordinary or decreased temperatures, and all of such compoundscanbe thionated by treatment with sulfur at either ordinary temperatures'or at tempeartures which may be up'to 180 C.' The products thusobtained have the formula i l whereE is oxygen or sulfur.

Also, those of the trivalent phosphorus compounds in which at least oneR is a haloalkoxy'r-adical, can be rearrangedby heating at a temperatureof 135-225 C.

' to give the'compounds The trivalent phosphorus halogen componentswhich are generally useful for reaction with an aldehyde and a tribasic,trivalent phosphorus ester has the formula atom of Y by anelementselected fromthe class consisting of ,O- and S and wherein two Rs takentogether stand fora radical seleeted from the class consisting of O-hydrocanbylene-O- and O-halohydrocarbylene- 'O 'r-adica1s which are freeof aliphatic uhsaturation and 7 contain from 2 to 10 carbon atomsThis'in'cludes comof preparing the compounds are 0 hexyl, phenyl, a

pounds of the following structures, where A denotes a hydrocarbylradical of from 1 to 12 carbonatorns or said hydrooarbyl radicalcontaining halogen and/or the allroxy radical as a substituent and-X ischlorine or bromine iP 's APX AQPX ASPX (A0) PX 2 2 (A0) (AS) PX zPX A(A0 PX A(AS) PX Particularly useful also are the dioxy compounds of theformula a O .t/ \LX wherein A is selected from the carbylene radiacls of2 to 10' carbon atoms and halogensubstitution products thereof.

Examples of trivalent phosphorus halogen compounds having the aboveformulas and useful for'the present 'purposes are, 'of course,phosphorus trichloride, phosphorus tri-bromide and mixed phosphorusbromide chlorides insofar as PX is concerned. 7

Compounds of the formula AOPX are hydrocarbyl or 1 halohydrocarbylphosphorodichloridites'or dibrornidites. The hydrocarbyl radical may bealkyl, alkenyl, alkinyl, cycloalkyl, aryl, alkaryl or aralkylandsuchhydrocarbyl radicals may be substituted with one or more atoms ofhalogen and/or alkoxy radiaclsl Examples of the phosphorodihalidites'aremethyl, ethyl, n-propyl, isopropyl,

allyl, n-bu-tyl, isobutyl, 2-propinyl, 3-e'thoxy-2-chloropropyl,dichlorododecyl 2,4-dichlorocyclopentyl, Z-bromo-Z- ethoxylcyclohexyl,Z-fluorocyclopentyl, Z-propoxycycloor ,B-naphthyl; 4-biphenylyl, benzyl,2- phenylethyl, l-isopropylbenzyl, 2-ethoxy-4-chlorobenzyl, oru-naphthylmethyl phosphorodichloridite and, phosphorobromidite.

Compounds of the formula A=SPX are phosphorodihalidothioites. Suchcompounds are, e.g., ethyl, n-butyl,

2 ethylhexyl, allyl, pentinyl, 2,4 dimethylcyclohexyl,

, 2-fluoroethyl, ethoxyoctyl, bromododecyl, or 4-biphenylyl Fphorochloridite, etc.,

phosphorodichloridothioite, etc.

The benzenoid phosphorodichloridites or phosphorodichloridothioites maycontain one or more halogen and/or alkoxy substituents'in either thearomatic ring thereof, at an aliphatic group whichis' attached to thearomatic ring, or at both the aromatic ring and said aliphatic group.fExamples of such halogen-substituted compounds are 2-, 3; or4-chlo'rophenyl" phosphorodichloridite orphosphorodichloridothioite and2-chloro-4- methoxybenzyl phosphorodichloridite or;phosPhorodichloridothioite. 1 a

Compounds of the formula. (AO) PX are dihydrocarbyl orbis(halohydrocarbyl) phosphorochloridites or phosphorobromidites. Suchcompounds are, e.g., the alkyl, alkenyl, or alkinyl esters such asdimethyl, diethyl, diallyl, diisopropyl, di-Z-pentenyl, -di-n-hexyl,di-n-heptyl, bis(2-ethylhexyl), di-n-octyl, tert-amyl n-dodecyl,phosbis(3-chloroallyl) bis(dichlorooctyl), bis(2-fluoroethyl), orZ-chloropropyl ethyl phosphorobromidite. 7 v

The corresponding phosphorohalidothioites which are useful for reactionwith an aldehyde and a triorgano phosphite to give the presentlyemployed polymer additives are 'e.g., dimethyl, diethyl, 'dipentinyl,'di-n-butyl, bis(2-chloroethyl), bis(3-fluoropropyl) or 2-propinyltrichlorobutyl phosphorochloridothioite or phosphorobromidothioite. r

Also presently useful are the cycloaliphatic esters such classconsistingof hydroas dicyclohexyl, dicyclopentyl,2,3-dimethylcyclohexenyl n-propyl, or bis(4-chlorocyclohexyl)phosphorochloridite or phosphorochloridothioite.

A class of aromatic trivalent phosphorus halides which are particularlysuited for the present purpose are the benzenoid dihydrocarbylphosphorohalidites, i.e., compounds of the formula Ar-OPX in which Ar isa benzenoid hydrocarbyl radical of from 6 to 12 carbon atoms and X ischlorine or bromine. Such compounds may be diaryl, bis(alkaryl),bis(aralkyl), aryl alkaryl, aryl aralkyl, or alkaryl aralkylphosphorochloridites, e.-g., diphenyl, bis(2 -butylphenyl), phenyl a-naphthyl, biphenylyl phenyl, 4 ethylphenyl phenyl, dibenzyl, or amylbiphenylyl phosphorobromidite.

The corresponding benzenoid dihydrocarbyl phosphorohalidodithioites,i.e., compounds of the formula wherein Ar is as defined above, aresimilarly valuable for the present purpose. Such compounds are, forexample, diphenyl phosphorochloridodithioite, p-tolyl 2-phenylethylphosphorochloridodithioite, etc.

An example of a mixed aliphatic-aromatic ester of present utility isn-butyl phenyl phosphorochloridothioite. Other examples of mixed esterswhich may be used are methyl phenyl phosphorochloridite, Z-ethyl-hexyl2,3- dichlorophenyl phosphorochloridite, etc.

Presently useful trivalent phosphorus halides also include theO-hydrocarbyl S-hydrocarbyl phosphorochloridothioites, i.e., compoundsof the formula -A A.S1I-X wherein A and X are as above described. Suchcompounds are, for example, O,S-diphenyl, or O-n-butyl S-p-cumylphosphorochloridothioites or phosphorobromidothicites.

A very valuable class of the presently useful halides includes thedihydrocarbylphosphinous halides, i.e., compounds of the formula A PXwherein A and X are as above defined. Such compounds are, e.g.,diethylphosphinous bromide, di-Z-butenylphosphinous chloride,bis(4-pentylphenyDphosphinous chloride, (dodecyl)phenylphosphinousbromide, etc.

Also useful in the reaction w'th aldehydes and triorgano phosphites arethe hydrocarbyl hydrocarbylphosphonohalidites andphosphonohalidothioites, i.e., compounds of the formula A AE-i -Xwherein A and X are as above defined and E denotes --O- or -S-. Examplesof such compounds are methyl, ethyl, Z-pentenyl, n-octyl, or biphenylylphenylphosphonochloridite or ethylphosphonochloridite, phenyl or ethylphenylphosphonochloridothioite, etc.

The above dihydrocarbyl phosphorochloridites,dihydrocarbylphosphorochloridodithioites, O hydrocarbyl S-hydrocarbylphosphorochloridothioites, dihydrocarbylphosphinous chlorides,hydrocarbyl hydrocarbylphosphonochloridites and hydrocarbylhydrocarbylphosphonochloridothioites may contain one or more halogensubstituents in either an alkyl ring, an aryl radical, at an aliphaticgroup which is attached to an aromatic ring thereof, or at both thearomatic ring and at said aliphatic group.

Another class of trivalent phosphorus halides which are presently usefulare the hydrocarbylphosphonous dihalides of the formula APX wherein A isa hydrocarbyl or halohydrocarbyl radical of from 1 to 12 car- 7 Mi bonatoms and X is halogen or bromine. Examples of such dihalides arephenylphosphonous dichloride, 2-, 3- or 4-chlorophenylphosphonousdichloride, isopropyl-,

n-butyl-, tert-butyl-, 2-butinyl-, triehlorobutyl-, andtert-dodecyl-phosphonous dichloride; o-, m-, or p-tolylphosphonousdichloride, cyclopentylphosphonous dichloride, etc.

Of pronounced utility are cyclic esters of phosphorohalidous acid. Suchesters have the formula wherein A is an alkylene or arylene radicalhaving from 2 to 10 cmbon ato-ms. Examples of compounds of the aboveformula are the various halo dioxaphospholanes, dioxaphosphorinanes, anddioxaphosphepanes, e.g., 2-chloroor 2-brorno-1,3,2-dioxaphospholane; 2chloro 4 chloromethyl 1,3,2 dioxaphospholane; 2,5 dichloro 1,3,2dioxaphosphorinane; 2,6,7 trichloro 1,3,2 benzodioxaphosphole; 2,5dibromo- 1,3,2 dioxaphosphorinane; 2 chloro 5 fluoro 1,3,2-dioxaphosphorinane, etc.

Any of the above described phosphorus-halogen compounnds can be reactedwith an aldehyde and a triorgano phosphite to give dior poly-phosphoruscompounds which are useful per se as polymer adjuvants or which may beoxidized, sulfurized or heat-arranged to give presently usefulcompounds.

The useful aldehydes have the formula ZCHO wherein Z is selected fromthe class consisting of hydrogen and hydrocarbyl, halohydrocarbyl,carboalkoxyhydrocarbyl, alkylthiohydrocarbyl, alkoxyhydrocarbyl andcyanohydrocarbyl radicals of from 1 to 12 carbon atoms, and the thienyland furyl radicals.

Owing to their easy availability, a particularly useful class ofaldehydes includes the aliphatic hydrocarbon aldehydes of from 1 to 18carbon atoms, e.g., formaldehyde, acetaldehyde, acrolein,propionaldehyde, butyr-' aldehyde, isobutyraldehyde, crotonaldehyde,valeraldehyde, isovaleraldehyde, hexanal, citronellol, heptanal, tiglicaldehyde, Z-ethylhexanal, octanal, 2-butyloctanal, propargaldehyde,G-methylheptaual, amylpropiolic aldehyde, decanal, undecanal,Z-methylundecanal, lauraldehyde, stearaldehyde, tridecaldehyde, etc.

The presence of cyano, halogen, alkyl, carboalkoxy, allcoxy andalkylthio-substituents in the aliphatic aldehyde has no effect on thecourse of the reaction; hence, there may be employed such substitutedfatty aldehydes as 3-cyanopropionaldehyde, chloroacetaldehyde,3-butoxybutyraldehyde, ethyl 4-formylbutyrate, diethyl formylsuccinate,iodoacetaldehyde, dichloroacetaldehyde, etc.

Presently useful alicyclic carboxaldehydes includecyclohexanecarboxaldehyde, 6 methyl 3 cyclohexenecarboxaldehyde, 4chlorocyclohexanecarboxaldehyde, etc. The heterocyclic aldehydes includefurfural and the thiophenecarboxaldenydes.

The presently useful benzenoid aldehydes may be aliphatic-aromatic orpurely aromatic aldehydes which may or may not be further substituted,e.g., benzaldehyde, 0-, mor p-tolualdehyde, phenylacetaldehyde,dipentylbenzaldehyde, cinnamaldehyde, 4-formylbenzaldehyde,phenylpropargaldehyde, 2-, 3- or 4-butoxybenzaldehyde, 0-, morp-chlorobenzaldehyde, p-(ethoxy)benzaldehyde, 2 ethoxybenzaldehyde, 3,4dipropoxybenzaldehyde, 4 (n butylthio)benzaldehyde, 4 bromo 4biphenylcarboxaldehyde, etc.

Triorgano phosphites which are generally useful with the aldehyde andthe phosphorus halide to give the presently useful esters may be simpleor mixed phosphites. Examples of useful phosphites are trimethyl,triethyl, triallyl, triisopropyl, tri-n-propyl, tri-Z-butenyl,tri-n-butyl, tri-tert-amyl, tri-n-hexyl, tri-n-heptyl,tris(.2-ethylhexy1), trioctenyl, tri-n-octyl, trinonyl, tridecyl,triundecyl, tribis(4-chlorobutyl) ethylphosphonite, phenylphosphonitebis(2-chloropropyl) n butylphospho- I phosphorus compoundschloro-B-methoxypropyl) and tris(2--romo-4-phenoxy-' butyl) phosphite.

7 Instead of the tribasic phosphites there may be em ployed as thetrivalent phosphorus ester component a diester of: a hydrocarbyl orhalohydrocarbylphosphonite,

e.g., a compound of the formula hydrocarhyl-?(O-al the hydrocarbyl' orthe and/or the alkoxy lryl); or those in which either alkyl radical orboth contain halogen 'radical as substituents. Presently usefulphosphonites include, e.g., dimethyl phenylphosphonite, diethyl 2-'propinylphosphonite, ethyl methyl phenylphosphonite, di-npropylmethylphosphonite, di-n-butyl benzylphosphonite, bis(2-chloroethyl) ptolyphosphonite, bis (2 methoxyethyl) cyclohexylphosphonite, allylpropyl 2,4-dichlorophenyiphosphonite, bis(trichlorooctyl)cyclohexylphosphonite, 'bis(4-fiuorobutyl) I 2 cyclohexenylphosphonite,bis(dischlorohexyl) nite, di-n-butyl pentachlorophenylphosphonite, etc.

Presently useful also as the triorgano phosphorus ester component arephosphinites of the (hydrocarbyl) PO-' alkyl or those in which eitherthe hydrocarbyl or the alkyl radicals of both contain halogen and/or'thealkoiry radical as substituents, e.g., allyl, butyl, or n-octyldiethylphosphinite or diphenylphosphinite, 4-methoxybutyl' or3-phenoxy-2-chloropropyl di n butylphosphinite 'ordi-fi-naphthylphosphinite; and the corresponding esters of thehalo-substituted phosphinic acids such as the 'methyl, pentyl, ethyl,Z-butenyl, Z-chloroethyl, 3-ethoxypropyl, or 4-butoXy-2-bromopentylesters of bis(4 chlorophenyl) phosphinite' or of n-butyl(4-chlorophenyl)phosphinite.

Reaction of any of the above phosphorus-halogen compounds with any ofthe aldehydes and any of the triorgano trivalent phosphorus compoundsgives products which are useful per se as adjuvauts for polymericmaterials generally, and such products may be further reacted withoxygen or sulfur or heat rearranged to 'give compounds containingphosphorus in only the pentavalent state and hence particularly suitablefor numerous polymer applications. V 1

As her'einbefore disclosed, the polymeric materials which are modifiedby the present phosphorus compounds are natural and synthetic, linearand cross-linked polymers.

Fibrous cellulosic pr oducts are prime'examples of the I 16; compounds,there. is not only flame-retardant efiect but also an improvement in thehand or feel of the fabric. In many instances, stability to light andheat is imparted to the natural polymers when the phosphorus'compoundsare used therewith in quantities which are too low to confer significantplasticizing or flame retarding effect, e.g., in quantities which are ofthe order of, say, from 0.1% to 5% by Weight of the polymeric material.

Synthetic polymeric materials, 1'.e., those. high mole- V cular weightmaterials which are not found in nature,

with which the present phosphorus compounds are ad vantageously employedmay be eitheralinear or crosslinked polymers and they may be eitherthose which are produced by addition polymerization or by condensation.

An important class of polymers which are beneficially modifiedaccording'to the invention are those obtained from a polymerizablemonomer compound having ethylenic unsaturation. 'Suchjmonomers have thegeneral formula C :C stituted by a member of the group consisting ofhydrogen, halogen, alkyL'aryl, aralkyl, alkaryl, alkenyl, alkinyl,cycloalkyl; haloalkyl, haloaryl, haloaralkyl, haloalkaryl, haloalkenyl,haloalkiny, nitroalkyl, nitroaryl, nitroaralkyl, nitroalkar'yl,nitroalkenyl, alkoxyalkyl, alkenyloxyalkyl, carboalkoxy, cyano, amido,dialkylamino, aldehydo, acyl, pryidyl, thienyl, furanyl, pyranyl,tetrahydrofuranyl, quinonyl, and higher heteroc'yclicgroups. Specificexarnples of the above radicals are methyl, ethyl, propyl, butyl,phenyl, tolyl, Xylyl, 4-ethylphenyl, beuzyl, 2-phenylethyl, vinyl,pr'openyl, butenyl, ethinyl, propinyl, butinyl, cyclopentyl,Z-methylcyclopentyl, cyclohexyl, chloro, fiuoro, bromo, 'iodo,2-chl0roethyl, chlorovinyl, 1,2-ch1oroethyl, Z-chlorophenyl,2-(4-chlorophenyDethyl, 4-brornobenz'yl, 'tropropyl, 4-nitrophenyl,'2-nitrobenzyl, ethoxy, methoxyethyl, vinyloxy, carboethoxy,

nitrovinyl, allyloxy, carbornethoxy, acetyl, propionyl, cyano, formyl,acetoxy,

propionoxy, carboxy, amido, furyl, carbazyl, indolyl, pyrized vinylandvinylidene compounds i.e., those having the CH =C radical. Compoundshaving such a radical natural polymeric materials which areadvantageously modified by the present'phosphorus compounds Thisincludes products made of cotton, linen, regenerated cellulose, kapok,hemp, wood and wood pulp, e.g., teX- tiles, twines, paper, cardboard,pressed board, batting Wood flour, sawdust, etc. Another group ofnatural poly mers of carbohydrate origin includes the starches such asthose derived from corn, barley, potato and cassava; Another class ofnatural polymers with which the present are beneficially used are thenatural gums, e.'g., agar, gum arabic, psyllium seed, tragacanth and gumkaraya, Natural rubber is also included. Naturalresins modified by thepresent phosphorus compounds include shellac, copal, damar, pine balsam,rosin,

etc. Proteinaceouspolymeric materials, e.g., animal glue,

. casein, Wool, and leather are also advantageously modi-' 'fied by saidphosphorus compounds. 'meri'c products,

generally, are rendered flame-retardant when'contacted with the presentphosphorus compounds ,in appropriate proportions, and worthy of specialcomment is the 'glow proofing of readily ignitible dusts and powdersprepared from the natural polymers. Plasticizing effectis conferred bythe present phosphorus 7 compounds to those of the polymers'which lackthe degrees of softness and flexibility that are required in theapplication for'which the polymers are destined. When cottonfibers ortextiles are treated with the phosphorus The natural polyvinylnaphthalene, 'divinylbenzene and are, e.g., the solid polymericalkenes, such as polyethylene, polypropylene, poly'iso bu'tylene orethylene-propylene copolymer; polymerized acrylyl and alkacrylylcompounds such as acrylic, chloroacrylic and methacrylic acids,anhydrides, esters, nitriles and amides, for eXample, acrylonitrile,ethyl or butyl acrylate, methyl or ethyl methacrylate, methoxymethyl or2(2-butoxyethoxy) ethyl methacrylate, 2(cyanoethoxy)ethyl3-(3-cyanopropoxy) propyl acrylate or methacrylate,2-(diethylamino)-ethyl or 2-chloroethyl acrylate or methacrylate,acrylic anhydride or methacrylic ahhydlide; methacrylamide orchloroacrylarnide, ethyl or butyl chloroacrylate; the olefinic aldehydessuch as acrolein methacroiein and their acetals;

the vinyl and vinylidene halides such as vinyl chloride, vinyl fluoride,vinylidene fluoride andl-chlorod-iluoro ethylene polyvinyl alcohol; thevinyl carboxylates such as vinyl acetate, vinylchloroacetate,..vinylpropionate, and .vinyl 2-ethylhexanoate;-theN-vinyl :imides such as N- vinylphthalimide and N-vinyls uccinimide; theN-vinyllactams such as N-vinylcaprolactam' and N- vinylbutyrolactam; thevinyl aromatic hydrocarbon compounds such as styrene, u-methylstyrene,2,4-dichlorostyrene, aor B- 7 vinylfiuorene; the vinyl ethers suchas'ethyl -.vinyl' ether or isobutyl vinyl ether; vinyl-substitutedheterocylic compounds such as vinylpyridine, vinylpyrrolidone,vinylfuran or vinylthiophene; the vinyl; or vinylidene'ketones such asmethyl vinyl ketone or' isopropenyl' ethyl ketone; vinylidenecyanideretc. Homopolymers of'the above compounds f or copolymers orterpolymer s' thereof are beneficially modified by the presentphosphorous compounds.

wherein the ethylenic group is sub-' 3 chloropropinyl, 3-niing theethylenic group, C=C are the homopolymers, copolymers and terpolymers ofthe :,fi3-Ol6fil1i6 dicarboxylic acids and the derivatives thereof suchas the anhydrides, esters, amides, nitriles and imides, e.g. methyl,butyl, Z-ethylhexyl or dodecyl fumarate or maleate, maleic,chloromaleic, citraconic or itaconic anhydride, fumaronitrile,dichlorofumaronitrile or citracononitrile, fumaramide, or maleamide;maleimide or N-phenylmaleimide, etc. Examples of particularly usefulcopolymers and terpolymers prepared from the a,/3-olefinic dicarboxycompounds are the copolymers of maelic anhydride and a vinyl compoundsuch as ethylene, propylene, isobutylene, sy'trene, a-methylstyrene,vinyl acetate, vinyl propionate, methyl isopropenyl ketone, isobutylvinyl ether, etc., the copolymers ofldialkyl fumarate such as ethyl orbutyl fumarate and a vinyl compound such as styrene, vinyl acetate,vinylidene chloride, ethyl methacrylate, acrylonitrile, etc.

Readily and advantageously modified by the present phosphorous compoundsare also the polymers and copolymers of unsaturated, cyclic esters ofcarbonic acid, e.g;, homopolymeric vinylene carbonate or the copolymersof vinylene carbonate with ethylenic compounds such as ethylene, vinylchloride, vinyl acetate, 1,3-butadiene, acrylonitrile,methacrylonitrile, or the esters of methacrylic or acrylic acid.

Advantageously modified by the present phosphorous compounds are alsopolymers, copolymers or terpolymers or polymerizable compounds having aplurality of double bonds, e.g., a rubbery, conjugated dienepolymerizate such as homopolymerized 2,3-butadiene, Z-chlorobutadiene orisoprene and linear copolymers or terpolymers such asbutadiene-acrylonitrile copolymer, isobutylenebutadiene copolymer (butylrubber) butadiene-styrene copolymer or 2-chlorobutadiene-vinylidenecyanide-acrylonitrile terpolymer; esters of saturated dior polyhydroxycompounds with olefinic carboxylic acids such as ethylene glycoldimethacrylate, triethylene glycol dicrotonate or glyceryl triacrylate;esters of olefinic alcohols with dica'rboxylic acids or with olefinicmonocarboxylic acids such as diallyl adipate, divinyl succinate, diallylfumarate, allyl methacrylate or crotyl acrylate and otherdi-ethylenically unsaturated compounds such as diallyl carbonate,divinyl ether or divinylbenzene, as well as the cross-linked polymericmaterials such as methyl methacrylate-diallyl methacrylate copolymer orbutadiene-styrens-divinylbenzene terpolymer.

Polymerized materials prepared by subsequent reaction of preformed vinylpolymers, e.g., polvinyl alcohol, the polyvinyl acetals such aspolyvinyl formal or polyvmyl butyral, or completely or partiallyhydrolized polyacrylonitrile, are likewise modified in properties by thepresent phosphorous compounds to give polymeric materials of enhancedutility.

Homopolymers and copolymers of the following polymerizable heterocycliccompounds are also advantageously modified by the present phosphoruscompounds: vinylpyridine, vinylfuran, vinyldibenzofuran,N-vinylcarbazole.

Polymeric materials with which the present phosphorus compounds can beemployed as adjuvants are also polymers which contain elements such assulfur, phosphorus, boron or silicon, e.g., the sulfides, sulfones,sulfoxides, sulfites, sulfates and sulfonates such as the polymers andcopolymers of vinyl sulfide, vinyl sulfone, 2-propenyl sulfoxide,ethylenesulfonic acid and its salts, esters and amides, and sulfonatedpolystyrene; the olefin-sulfur dioxide polymers, the phosphines,phosphites, phosphates and phosphonates such as diphenylvinylphosphine,a'llyl phosphite and metallyl phosphite, ethylenephosphonic acid andstyrenephosphouic acids and their salts, esters and amides; the silanessuch as dimethylvinylsilane, diphenylvinylsilane andmethylphenylvinylsilane, etc.

A class of synthetic polymeric materials with which the presentphosphorus compounds are very useful comprises the cellulosederivatives, e.g., the cellulose ester such as cellulose acetate,cellulose triacetate, butyrate, the cellulose ethers such cellulose,cellulose nitrate, csrboxymethyl cellulose, cellophane, rayon,regenerated rayon, etc. The phosphorus compounds may be incorporatedinto films of such cellulose derivatives by adding them to the solutionsfrom which the films are cast or into the melts from which the fibersare extruded.

The present phosphorus compounds are particularly suited to themodification of liquid resin compositions of the polyester type. Suchresins are well adapted in structural fabrications, particularly in themanufacture of reinforced fibrous structures, e.g., glass or cellulosicfibers. However, their usefulness in such applications has been hamperedby considerations of the fire hazard which stems from theircombustibility. It has been found, according to the invention, that thepresent phosphorus compounds are flame retardants for the polyesterresins, and that they impart the flame retardant property atconcentrations which do not sacrifice of transparency or flexibility.The present compounds are compatible with the polyesters in proportionsWhich not only impart fireproofing prop erties to the resins but alsoserve as softening and plasticizing agents. Polyester resins with whichthe present phosphorus compounds are useful are either the linearpolyesters which are obtained by the reaction of one or more polyhydricalcohols with one or more a,,B-unsaturated polycarboxylic acids alone orin combination with or celluose acetate one or more saturatedpolycarboxylic acid compounds, or

the crosslinked polyester resins which are obtained by reacting thelinear polyester with a compound containing a CH =C group.

Polyhydric alcohols which are used for the preparation of the presentlymodified polyester resin are, e.g., ethylene glycol, diethylene glycol,propylene glycol, trimethylene glycol, trimethylo'lpropane,trimethylolethane, 1,4-butanediol, 4,4-isopropylidenediphenol,4,4-isoproplidenedicyclohexanol, hydroquinone, 1,Z-dihydroxynaphthaleue,4,4- dihydroxybiphenyl, 4,4-(Z-butylidene)-di-m-cresol, glycerol,pentaerythritol, mannitol, etc.

The polycarboxylic acid compounds used in preparing the presentlymodified polyester resins are, e.g.,' the 0:,5- unsaturated acids or theanhydrides or acyl halides thereof, such as maleic acid, maleicanhydride, maleyl chloride, fumaric acid, itaconic acid, itaconoylchloride, mesaconic acid, citraconic acid, etc.; the alkanedicarboxylicacids, anhydrides or acyl halides thereof such as oxalic or malonicacid, anhydride or acyl halide, succinic acid, anhydride or halide;adipic acid, acyl halide or anhydride and sebacic acid, acyl halide oranhydride; the cycloparafindicarboxylic acids such as1,2-cyclohexanedicarboxylic acid or its anhydride or acyl halide; thearomatic dicarboxylic acids such as phthalic, terephthalic or 1,2-naphthalenedicarboxylic acid or the anhydrides or acyl halides thereof,the halogenated dicarboxylic compounds such as dichloroterephthalic acidor l,4,5,6,7,7-hexachlorobicycle-(2,2,1)5-heptene-2,3-dicarboxylicanhydride, etc.

The cross-linking component of the present modified polyester resin maybe any compound containng the group CH =C and having a boiling point ofat least 60 C. Among the numerous compounds which are employed for thispurpose may be mentioned styrene, ethyl acrylate, methyl methacrylate,acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloroacetate,isopropenyl methyl ketones, isobutylene, vinyl isobutyl ether,N-vinylpyrrole, acrolein, 3-butenyl acetate, et

The present phosphorus compounds may be added to the polyestercompositions at any stage of processing. For preparation of casting andlaminating resins, a recommended procedure is to first prepare a resinsyrup by reacting the polyhydric alcohol component with thepolycarboxylic acid component and then to add the phosphorus compound toa mixture of the resin'syrup and the cross-linking agent i.e., the vinylor vinylidene compound, previous to curing. This latter step isgenerally as methyl or ethyl f hydric compound. 7 the curing orhardening .step

hesiv'e, and for, the production ofhard' foams.

' w h re e oy assess;

t-b yl' dr pe oxide n t pt se o di: tives such as mold lubricants,reinforcing agents, pigments, etc. Use of the present phosphoruscompounds in amounts of, say, to 25%, based on the weight of thepolyester, has been found'to'impart flame retardant properties to thepolyester resins, and when the phosphorus compound is employed ingreater proportion, say, up to an equal amount by weight of thepolyester, there is also evidenced very good plasticizing elfect. Atvery low concentrations, say at concentrations of up to 5% based on theWeight of the polyester, increasein thermal stability and decrease inlight sensitivity are noted.

The present phosphoruscompounds are useful for modifying either the castpolyester resins or fibers and foams prepared frompolyester resins. lhecompounds e nz y o id yl me y ks on pe oxide r are preferablyincorporated into the reactant mixturev previous toesterificationreaction or they may be added to the ejection mix as inthe case of fiber manufacture or to the foam mix prior to hardening.Good results'can be obtained, however, by application of the phosphoruscompounds to the. finished fibers or foams, e.g., by immersing orspraying the polyester, fibers or textiles prepared therefrom in orwith'solutions of the phosphorus compounds or by similar treatment ofthe polyester foams. V V

-The present phosphorus compounds are also valuable adjuvants' forfilm-forming polyesters which may or may not be modified with drying orsemi-drying fatty. oils or terpenic compounds. These types ofpolyesters, commonly known as alkyd resins, are plasticized by thephosphorus compounds. fore contacting'with the present adjuvant or thephosphorus compound maybe incorporated into the resin by adding thecompound'to the mixture of polyhydric' alcohol, polycarboxylic acid and/or oil or terpenic compound before the resinifying esterificationreaction is eftested, j, a V

The epoxy resins are another class of polymeric materials with which thepresent compounds are compatible and are advantageously used.- Theseresins are condensation products formed by the reaction of a polyhydroxycompound and epichlorohydrin, nets are subsequently cured by agents. Thehydroxy compound hydric compounds mentioned above as usefulfor theaddition of cross-linking preparation of polyester resins; bisphenol,i.e.,'4-,4'-iso-1 propylidenediphenol, is the commonly employed polymaybe a dicarboxylic compound such as phthalic anhydride oradipic acid, but

moi p-phenylene diamine QI diethyIenetriamine, The

to the linear condensation productof the epichlorohydrin and thepolyliydnic compound, together with the crosslinking agent, previous tocuring or hardening. The resulting'r'nixture is then cast into molds orit may be used for the manufacture'of laminates, as bonding adlat teruse, the mixture of linear condensation product,

The resins may be preformed bewhich condensation prod- The cross-linkingagent employed in andat least two reactive hydrogen atoms, i.e.,hydrogen atoms determinable by the Zerewitinofl? method. The usefulactive-hydrogen containing compounds may be polyesters prepared frompolycarboxylic acids and polyhydric alcohols, polyhydric polyalkyleneesters having at least 2 hydroxyl groups, polythioether glycols,polyesteramides, etc. 7 3

The polyesters used for the production of the polyurethane may bebranched and/or'linear. Thus, the use-' 'ful polyesters and/0rpolyesteramides may include those obtained by condensing' any polybasic(preferably dibasic carboxylic) organic acid,'such as adipic, sebacic,6-.aminQ- caproic, phthalic, isophthalic, .terephthalic, oxalic,malonic, succinic, maleic, cyclohexane-l,Z-dicarboxylic,cyclohexanel,4-dicarboxylic, polyacrylic, naphthaleneTLZ-dicarboxylic,fumaric, itaconic, etc., with polyalcohols such as ethylene glycol,diethylene glycol, pentaglycol, glycerol, sorbitol, triethanolamine,di-(fl-hydroxyethyl) ether, etc. and/ or amino-alcoholssuch asethanolamine.

The alkyleneglycols and polyoxyalkylene or polythio-. alltylene glycols.used for the production of the polyurethanes may comprise ethyleneglycol, propylene glycol, butylene glycol-2,3,butylene glycol-1,3,Z-rnethylpentanediol-2,4, 2-ethylhexanediol-.1,3, hexamethylene glycol,styrene glycol and decamethylene glycol, etc.

' The organic polyisocyanates useful for the production of thepolyurethanes include ethylene diisocyanate, ethylidene diisocyanate,propylene-1,2-diisocyanate, butylene-l,

3-diisocyanate, hexylene-1,6-diisocyanate, eyclohexylene-1,2-diisocyanate, m-phenylene diisocyanate, 2,4-toluylene'diisocyanate', 1,6-toluylene diisocyanate, 3,3'-.dimethyl-4,

' diisocyanate, etc.

may be any of the polyl is more generally a polyamine such as ethylenediamine, V V

For the a phosphorus compound and cross-limting agent is cured V thepresence of blowing agents. The hardenedprod; 'ucts, whether moldedcasts, laminates,'or foams are characterized a by possessing flameretardant propert es and g'ood'dimensional stability,

The polyurethanes comprise another class of polymeric materials whichare beneficially modified phosphorus. compounds. The polyurethanes,liige the above mentioned polyesters, are commercial materials sulatingfoams,

by the present.

, 25% byweight of-the polyurethane.

' in practice, the polyurethane plastics are produced by bringingtogether the organic compound whichcontains at least 2 reactive hydrogenatoms and is capable of orming polyurethanesfwith the polyisocya'nate'and an activator mixture. The latter is made up of atleast onecross-linking agent and/or an accelerator and may contain, if desired,added water or anaqueous solution. The addition of such an activatormixture to -the mixture of polyisocyanates and active hydrogen compoundinitiates the cross-linking action needed to obtain homogeneous plasticsor the 'c'ross linking. and foaming jaction necessary to obtain foamplastics. Useful cross-linking agents, in.- clude water or aqueoussolutions for foamed plastics and the polyalcoh ols, 'such as ethylene.glycol, glycerol, etc. for non-porous plastics; and useful acceleratorsinclude the tertiaryamine's. "j V s For preparation of the with "theactivator mixture, i.e., before hardening. The

hardened molded pieces'of foams are rendered flame retardant by theinclusion 'therein of the, present phosphorus compounds in quantities.of, say, from 5% to Simultaneous plasticizing property'is evidenced: andcontinues. to be demonstrated until the quantity of phosphorus compoundis substantially equal to that of the polyurethane. Use of thephosphorous compounds in-"the'polyurethanefoams can also increaseflexibility and,

in'structu ral applications e.g., as in- H in the manufacture of textilefibers, as r resins'bases inthe manufacture of curabgle coating coinipositions and as impregnating adhesives in the fabric a- '75 e V in'some applications, improve the mechanicalprop'erties of'thefoams.

Phenolic resins are also beneficially modified 'by the presentphosphorus 'conipounds,{which compounds are incorporated 'into the resineither by milling inmolding "applications or by. addition tofilm-forming or impregnating and bonding solutions previous topast-ing.Phenolic polyurethanes are condensation products.

flame-retardant polyurethanes,

resins with which the present compounds are employed are, for example,the phenol-aldehyde resins prepared from phenols such as phenol, cresol,xylenol, resorcinol, 4-butylphenol, 4-phenylphenol, and aldehydes suchas formaldehyde, acetaldehyde, or butyraldehyde in the presence ofeither acidic or basic catalysts, depending upon whether the resin isintended for use as a molding or extruding resin or as the resin base incoating and impregnating compositions. When destined for use as moldingresins the phenol is generally condensed with the aldehyde in thepresence of alkali, and the present phosphorus compound is added to theresulting liquid resin previous to the curing stage. When the phosphoruscompound is used in greater proportions, say in proportions of from to30% by weight of the resins, significant flame retardant properties areevidenced, which properties are accompanied by plasticizing effect. Inhigher ratios these effects are preserved, although the higherproportions of phosphorus compounds are not particularly recommendedowing to economical considerations.

The aminoplasts comprise another group of aldehyde resins which arebeneficially modified by the present phosphorus compounds. Examples ofthe aminoplasts which are modified according to the invention are theheat-convertible condensation products of an aldehyde with urea,thiourea guanidine, cyanamide, dicyandiamide, alkyl or aryl guanamines,and the triazines such as melamine, 2- chloro-4,6-diamino-1,3,5-triazineand 2-hydroxy-4,6-diamino, 1,3,5-triazines. The aminoplasts may beprepared by using various aldehydes instead of formaldehyde; e.g., theremay be used acetaldehyde, propionaldehyde, furfural, glyoxal and thelike.

The present adjuvants are compatible with the aminoplasts; and dependingupon the quantity of phosphorus compound used, they serve to plasticizethem, and to render them fire-retardant. When the aminoplasts aredestined for use as impregnating agents, bonding adhesives, coatings andcasting of films, the phosphorus compounds are incorporated intosolutions or suspensions in which the aminoplast is carried. Theresulting mixtures give strong, fire-retardant laminates when sheets ofpaper, glass cloth or fabric are impregnated therewith and cured.Textile fabrics or papers to which the liquid mixtures are applied bypadding or spraying are not only made fire-retardant but also renderedpliable and shrink-proof. Wet strength is increased. In moldingapplications, the phosphorus compound is compounded with the resintogether with the customary dyes or pigments and fillers, e. g.,cellulose, asbestos, wood flour, glass fibers, chopped cotton fabric.

Also beneficially modified by the present phosphorus compounds are thenylons, i.e., the superpolyamides which are generally obtained by thecondensation of a diamine, e.g., hexamethylenediaminc with adicarboxylic acid, e.g., adipic acid. Depending upon the quantity ofphosphorus compound employed and the individual nature of the compound,there are obtained flame-retardant, dye receptor, and/ or plasticizingeifects.

Other polyamides with which the present phosphor-us compounds arebeneficially employed, e.g., for improvement in thermal stability, arethe polypeptides which may be prepared, e.g., by the condensationreaction of an N- carboalkoxy substituted or an N-acyl substituteda-amino carboxylic acid with the same or different unsubstituted aminocarboxylic acid, e.g., by reaction of N-carbobenzyl oxyglycin withglycine or a mixture of glycine and lysine, or an N-carboxy amino acidanhydride such as N-carboxy-DL-phenylalanine anhydride.

Still another class of polyamides which are beneficially modifiedaccording to the invention are the polymeric lactams, e.g.,polycaprolactam, piperidone, 2-oxohexamethyleneimine and other cyclicamides. The present phosphorus compounds can be incorporated intomolding or extruding compositions for plasticizing and flameretardanteifect and/ or to serve as mold lubricants.

The present phosphorus compounds are also advanta-;

alcohols such as ethylene glycol, propylene glycol or hexamethyleneglycol; the polyesters which are obtained by the self-condensation ofhydroxy acids such as lactic acid or 4-hydroxybutyric acid, thepolyamides which are prepared by the self-condensation of aminocarboxylic acids such as 4-aminobutyric acid or 6-aminocaproic acid; thepolyanhydrides which are formed by the self-condensation of dicarboxylicacids such as sebacic acid or adipic acid, etc. The present phosphoruscompounds are plasticizing flame-retardants for such self-condensationproducts, generally; and where transparentizing effect and dyereceptivity are lacking, the present compounds are often instrumental inameliorating such deficiencies.

The present phosphorus compounds are likewise advantageously employedwith the silicone resins, i.e., the linear polymers which have therepeating unit:

Example 1 This example shows the preparation of flame-retardantpolyvinyl acetate by incorporating therein the following diorpolyphosphorus compounds:

onaorrolonionr o omi 0 onii 0 onionolonm o CHQGHCICHS (2) 0 0H: 0(OH3QHC1OH20)ZPOCH i=0 JH-l" 00111011010113), n3 0 CHnCHClCHsJz(ClCHzOHzO):P 0 our 0 OHICHQGI):

phenyl (ClCH2CHiO)2P 0 OHP o CHaOHZODR Hm Ha (OlGHaOHzO)zP 0 our 0CHzCHzCl):

oiomoniom o oni o uni 0 omomoi Ha O CHQCHQOI O CH:

onaonownionro 0111" 0 (ire-1 o 0112011010113):

Ha o oniouoiona 25 Example 2 The flame retardant effect of the presentphosphorus compounds on polyacrylonitrile (trademarked Acrilan) wasascertained by adding the compound to a dimethylformamide solution ofthe poly acrylonitrile, casting films from the resulting mixtures,removing the solvent by drying under the heat lamp, and then testing forflame-proofing by holding the films just outside of the outer cone ofthe Bunsen burner flame. The compounds 6, 7, 8, 19 and 29-31 of Example1, each employed in a quantity which was 25% by weight of the totalsolids, were thus tested. In each case slight charring occurred, but noignition to flame. On the other hand the flame of a Bunsen burner jumpsfrom the burner to a fllm of polyacrylonitrile, alone, when the latteris held near the burner flame. The flame-proofed films of this examplewere all flexible, clear and colorless. No exudation was noted on thefilm surfaces and no haziness was evidenced in tests of the filmsconducted with the Photovolt reflection meter.

Example 3 The compounds l-l0, 12-18, 20, 21, 25, 28 and 30-32 of Example1 were evaluated as flame retardants for homopolymeric ethylmethacrylate. Testing was conducted on films prepared by casting acetonesolutions of the homopolymer to which solutions there had beenrespectively added one of the above compounds in a quantity equal byweight to the polymer content of the solution. After thorough removal ofthe solvent the films were tested by holding them just outside of thesurface of the Bunsen burner flame. None of them ignited. When each ofthe films was held in the flame, combustion did occur, but it ceased assoon as the film was removed from the flame. Use of the presentcompounds had thus rendered the polymer self-extinguishing.

Example 4 To a 10% solution of polyvinylidene chloride (known to thetrade as Saran) there was respectively added one ClCHz CICHsCHB I 01120Example 5 To 10% solutions of polyvinyl chloride in cyclohexanone therewas respectively added each of the compounds 2, 9, 11 and 34 of Example1 in a quantity which was by weight of the polyvinyl chloride content ofthe solution.

Films were cast from the resulting solution and the solvent evaporatedby air drying at room temperature for about 24 hours. The films thusobtained were clear, colorless, and free of surface exudation. When theywere brought to the surface of the Bunsen burner flame, they charred butdid not ignite into a flame. When removed from the flame, burning ceasedi.e., they were self-extinguishing.

26 Example 6 The compounds 2, 8, 9, ll, 19, 29, 30, 32, 33 and 35 ofExample 1 were respectively added to 5% solutions of a polyvinyl formal(Pormvar) in ethylene dichloride.

The phosphorus compound was used in a quantity which was 25% by Weightof the total solids content of the solution. Films cast from theresulting mixture were clear and colorless after air-drying for 24hours. No surface exudation was noted. When tested for flammability byholding the films just outside of the outer cone of the Bunsen burnerflame, there occurred slight charring but no ignition to flame. Films ofpolyvinyl formal alone, i.e., controls prepared in absence of thephosphorus compound, burst into flame under the same circumstance.

Example 7 To a 10% benzene solution of polystyrene there wasrespectively added each one of the compounds 4, 7, 11, 12, 19, 21-24,26-28, 30, 31, and 33-35 of Example 1 in a quantity calculated to be 10%by Weight of the total solids content.

Films cast from the resulting mixtures and air-dried at room temperaturefor 24 hours were colorless, transparent and free of haziness asdetermined by the Photovolt reflection meter. No exudation was presenton the film surfaces. They were tested for flammability by holding thefilm just outside of the outer cone of a Bunsen burner flame. When asimilarly prepared film from styrene alone, i.e., one containing noadditive, is held in this position, it instantly bursts into flame. Onthe other hand, films prepared from mixtures containing the 10%concentration of any one of the above phosphorus compounds, as hereindescribed, melted and charred somewhat but did not ignite into flame.

Example 8 This example shows testing of the following compounds asflame-retardant additives for polystyrene:

where n is 0.5.

where n is 0.5.

Each of the above compounds was respectively added to finely groundpolystyrene granules in a quantity equal to 5% by weight of thepolystyrene by blending for 15 minutes in a tumbling type laboratoryblender and the mixture extruded through a 1" single screw extruder at400 F. into 7 rods.

The extruded rods were then subjected to repeated (3) ignition with aBunsen burner flame for 15 second periods in a draft-free hood. Aftereach ignition period, upon removal of the flame, the extruded rod wasfound to be immediately self-extinguishing whereas a control rod, i.e.,a similarly extruded rod of polystyrene containing none of the abovecompounds, continued to burn rapidly, drip flame, and emit heavy blacksmoke after the first ignition period.

Example 9 The following compound was tested for flame-retardant effectin polystyrene foam:

ll (CH GHBrGH2OhPOCHP (oomonnrcmn HZCHB The compound was incorporatedinto the pneumatogen styrene copolymer containing 2.7 filled granularpolymer at a concentration by blending for 15 minutes in a tumbling typelaboratory blender and the composition extruded through a 1" singlescrew blender at 300 F. The resulting 1%" diameter polystyrene foamcylinder was cut into 12" lengths and conditioned in (ClcHzOHBrOHzOhP oGHPO on a circulating oven at 70 C. for 48'hours to devolatilizeresidual pneumatogen. The cylinder was then subjected to repeated (3)ignitions with a Bunsen burner flame for 15 second periods in-adraft-free hood. After each ignition period, upon removal of the flame,the cylinder was foundto be immediately self-extinguishing; whereas acontrol cylinder, i.e., a similarly extruded cylinder of polystyrenefoam containing none of the above compound, continued to burn rapidly,drip flame, and emit heavy black smoke after the first ignition period.

Example .To' a 10% solution of a 50:50 molar ratio styrene-methylmethacrylate copolymer in benzene there was respectively added one ofthe compounds 2, 7, ll, 12, 19, 23, 26-29, 31 and 33-35 of Example 1, ina quantity which was calculated to be 25% by weight of the totalsolidscontent. The resulting mixtures were cast into films and the filmsweer air-dried for 24 hours. Observation of the films at that timeshowed them to be flexible, clear and colorless, and the film surfaceswere free of exudation. Evaluation on the Photovolt reflection meterdisclosed no haziness. .The films did not ignite into flame when heldjust outside of the outer cone of the Bunsen burner flame, whereas filmsprepared from the copolymer alone burst into flame when so positioned. 7

Example I] H V The compounds.2l2, 19, 22, 23, 26, 33 and 35 of Example 1were respectively added to 10% solutions of a 72:28styrene-acrylom'trile copolymer in methyl ethyl ketone.

by weight of the total solids. Films cast from the resulting solutionswere clear, colorless, and free of'surface exudation. When, tested withthe Photovolt reflection meter no haziness was noted. The films flamedonly when held in the open, luminous flame of the Bunsen burner, butwhen they were removed from the flame, burning ceased, i.e., the films.

were self-extinguishing.

Example 12 The compounds of Example 8 were tested for flameretardanteffect in a blend of polystyrene and butadienestyrene copolymer whichblend consisted of 6.5% by weight of the copolymer.

The compounds were respectively incorporated into the granular blend atof compound I and at respective concentrations of 3.75% and, 7% ofcompound II by blending for 15 minutes in a tumbling-type laboratoryblender. The mixture was then extruded through a 1'? i F. into rods.

'f I The extruded rods were then subjected to repeated ,(3) ignitionswith a Bunsen burner flame for 15' second periods in a draft-free, hood.After eachignition period, upon removal of the The phosphorus compoundwas used in- V a quantity which was 25% a concentration of 4% by weight.

single screw extruder at 400 flame, the extruded rods were 28 7 Example13 This example shows testing of the following compound as aflame-proofing agent for a 72:28 Weight ratio styrene-butadienecopolymer known to the trade as SBR rubber:

where n has an average value of 0.5.

A mixture consisting of 84.2 parts by weight of the copolymer and 15.8parts by weight of the above compound was milled into a sheet on a cold,two-roll polymer mill, and a portion of the sheet was pressed into a 2.5x 0.25" x 0.040 test specimen on the Carver press (4000 p.s.i.;temperature of the platens, 130 C.). Testing of the milled sheet and ofthe pressed test specimen for flame retardancy showed both to beself-extinguishing, i.e., combustion occurred only While they were heldin the Bunsen burner flame and ceased immediately upon withdrawal fromthe burner flame. On the other hand a milled sheet or a similarlypressed test specimen of the copolymer, alone, continued to burn afterwithdrawal from the Bunsen burner flame, 0.5 inch of the test specimenbeing consumed in 21 seconds.

Example 14 H (CHaOHgCHClCHiO)POCHP(OCH2CHC1QH2GH3)Z HgOHgCHaphenyl-P[OOHP(OGH2CHO1OH3)2 among 2 (CH3OHCIOH20)2POCHP(OCHzQHC1CH3 z 7CHBlOHzBI The following mixtures were respectively milled into sheets:

parts by weight of copolymer l5 parts by Weight of (A) parts by weightof copolymer 10 parts by weight of (B) 86.6 parts by weight of copolymer13.4 parts by weight of (C) not jump to the tests,'whereas the burnerflame jumped to and ignited similarly positioned'and prepared conof thecopolymer, alone. Also, while either the sheeted or molded test samplesignited when they touched found to be immediately self-extinguishing;whereas a similarly extruded blend of polystyrene and butadienenone ofthe above compound continued to burn rapidly, drip flame, and emit heavyblack smoke after the first ignition period;

(QlGHgCHBrCHzOhP OCHP OCH the. outer cone of the Bunsen burner flame,ignition ceased as soon as the samples were removed from the edge of theburner flame. 7

Example 15 V V This example shows testing of the following com- 7 poundsas flame-retardants for polyethylene:

H P (oomonnromon) drying for 24 hours the ture for 24 hours. I colorlessand transparent.

tCH CHgCHC1CH2O)P O CH? CHzCHClCHrCHah CH UH2CHCICH2-P O CHP (OCH2CHC1CH2CHa)2 CHzCHzOHClCHzO H The compounds were respectively milled,at 170 C. on a 2-roll plastic mill, with a polyethylene having anaverage molecular weight of ca. 20,000, in quantities calculated to giveeither 8.2% by weight of (A), or 11.2% by weight of (B), or by weight of(C) based on the total weight of polyethylene plus phosphorus compound.The milled sheets thus obtained were respectively pressed at 170 C. onthe Carver press into 2.5 x 0.25 x 0.040" test specimens. When the testspecimens were held in the flame of the Bunsen burner they were notreadily ignited and upon withdrawal from the burner flame, combustionceased at once, i.e., the test specimens were self-extinguishing. On theother hand a like-dimensioned specimen of polyethylene, alone, isreadily ignited and continues to burn after withdrawal from the burnerflame.

Example 16 The compounds 1-12, 18, 28, 29, 32, 33 and 35 of Example 1were evaluated for use as plasticizers for polymeric ethyl methacrylate.Each of said compounds was respectively added at room temperature to asolution of the polymeric methacrylate in a quantity which was equal byweight to the quantity of the polymer, and films were cast from theresulting mixtures. After airfilms thus obtained were clear, colorless,and flexible; there was no evidence of oily exudation. Testing of thefilm by means of the Photovolt reflection meter showed no haziness.

Example 1 7 The compounds 1-9, 11, 13-15, 19, 21, 33 and 35 of Example 1were evaluated as plasticizers for polyvinyl acetate; To a 10% solutionof the polyvinyl acetate in ethylene dichloride there was respectivelyadded an amount of one of the said compounds which was equal by weightto that of the polyvinyl acetate. Films cast from the resulting mixtureswere dried at room tempera- The films thus obtained were flexible, Nohaziness was observed with the Photovolt reflection meter, and noexudation of the phosphorus compound was present on the film surfaces.

Example 18 To a 10% solution of polyacrylonitrile in dirnethyl formamidethere was added an equal weight, based on the polyacrylonitrile, of oneof the compounds 13, 16, 17, 21, and of Example 1. Films cast from theresulting mixture were air-dried 24 hours using a heat lamp. Thesoftened, flexible films which were thus obtained were clear andtransparent and colorless. Testa ing of the films with the Photovoltreflector meter disclosed no haziness and retention of the phosphorusadditive was shown by lack of any exudation on the film surface.

Example 19 Films were cast from 10% cyclohexanone solutions of polyvinylchloride to which had been respectively added at room temperature aquantity of one of the compounds 22, 26, 27, 30, 31 and 34 of Example 1which was equal by weight to the weight of the polyvinyl chloride.

The solvent was allowed to evaporate from the film, and after 24 hoursthe film was tested for haziness by the Photovolt reflection meter andfor exudation of plasticizer by noting surface oiliness. The flexible,colorless transparent film was found to be entirely free of haze and noexudation of the phosphorus compound was evidenced.

Example 20 (")/O CHzCHzCl phenyl-P[(|) CHP\ CHzCHs 0 0112011201 2 Thecompound was added in the required quantity at room temperature to a 10%solution of the polymer in methyl ethyl ketone and films were cast fromthe resulting mixture. Observation of the films after air-drying at roomtemperature for 24 hours showed them to be flexible, clear, andcolorless and free of exudation. No haziness was determined on thePhotovolt reflection meter.

Example 21 The compounds 1, 2, 3, 6-9, 11, 14, 16, 21, 25 and 29 ofExample 1 were tested as adjuvants for a polyvinyl formal known to thetrade as Formvar.

Testing was conducted by respectively adding to a 5% ethylene dichloridesolution of the polymer a quantity of one of the above compounds equalby weight to that of the polymer, casting films from the resultingmixtures and air-drying the films at room temperature for 24 hours. Thefilms thus obtained were flexible, clear and colorless. Testing in thePhotovolt reflection meter disclosed no haziness and there was nosurface exudation.

Example 22 Example 23 This example shows plasticizing of a 72:28 weightratio styrene-acrylonitrile copolymer. Each of the compounds 2, 7-9, 11and 35 of Example 1 was respectively added to a 10% solution of thecopolymer in ethylene dichloride. A quantity of one of said compoundsequal by weight to the copolymer was used. Films cast from the resultingmixture were found, after air-drying at room temperature for 24 hours,to be flexible, transparent and colorless. Testing of the clarity by thePhotovolt reflection meter disclosed no haziness and good retention ofthe phosphorus compound was evidenced by lack of surface exudation.

Example 24 The compounds 2, 4, 5, 7, 9, 11, 22, 23, 26, 29, 31, 33 and35 of Example 1 were tested for use with a 55:20:25 weight ratiostyrene-acrylonitrile-2-ethylhexyl acrylate copolymer.

Films cast from a 5% benzene solution of the copolymer to which solutionhad been added an equal weight, based on the copolymer, of one of saidcompounds were allowed to air dry for 24 hours and evaluated. They werefound to be flexible, transparent and colorless. Testing with thePhotovolt reflection meter disclosed no haziness and the surface of thefilm showed no oily exudation.

' spectively added to a 15% 31 Example 25 The compounds 1-9, 11, 1349,28, 33' and 35 of Example 1 were tested as plasticizers for the 1:1molar ratio copolymer of maleic anhydride and vinyl methyl ether orethylene. Each phosphorusjc'ompound was resolution of the ethylenemaleicanhydride copolymer in acetone and to a 7% solution of the vinyl methyl'ether-maleic anhydride copolymer in dimethylforrnamide. The quantity ofphos phorus compound employed in each instance was equal by weight tothat of the copolymer present in the solu surfaces.

' 'Using the above procedure, there were also prepared similarly goodfilms from 1:1 weight ratio mixtures of said vinyl methyl ether-maleicanhydride copolymer and the compounds 21, 22 and 25 of Example 1. 7 j

Also, similarly, good'films were obtained when the 6 above procedure wasemployed with 1:1 weight ratio mixtures of said ethylene-maleicanhydride copolymers and one of the compounds. 7 g

7 Example 26 V This example shows the stabilizing effect of the presentphosphorus compounds on polyvinyl chloride. Variousphosphite-phosphonates were tested in the following formulation:

Parts by weight Polyvinyl chloride 100 Dioctyl phthalateul 50Barium-cadmium' lau'rate; '2 Phosphite-phosphonatm, 0.25

The ingredients were mixed' in a glass vessel and the resulting mixturesmilled on the two-roll mill for three minutes at 170 C., sheeted, cooledand then molded into sheets. Molding was conducted according to themethod described at pp. 36 of Polymer Evaluation Handbook, U.S.Department of Commerce,0tfice of Tech- 7 nical Services, 1956 (W.A.D.C.Technical Report 56-399,

ASTIA document No. AD 110557, PB 121870), wherein molding is eifectedbetween heated platens at an initial pressure of 500 p.s.i. and a finalforce of 7 tons on a 6" x 6" area. After allowing the molded sheets tocool, specimen strips were cut therefrom and exposed in a circulatingair oven at 150 C. for 5 .hours. No change in color was observed insamples containing any one of f the following phosphorus compounds:

' u 7 V (OlOH2CHzO) 2POCHP(O omomop H3 7, V,

goiomomonrooni ojomonlona V 7 I phenyl V 1 0 H (olomoiruonrooHiwomQHzoDz V o '1 7 a. (omonoiomouzrooni oomorfoiomu mom o1on ono V 7 7 7s f o i m omens CHrO V phenyl 7' sure (approx. 172 C.), 0

o1oBzoHo or PQCHi W C a): CHrO but ll oionzomonroonr o CHzQHrCl):

' H2CH2Q s ll (ClQHzCHzOhPQ CHI (0 CHaCHzOl):

nzongomom O CH2 Hz, h n r-onrooni [001123 j phenyl momomona 2 u A(CHaGHClCHzOhPOCHE(OCHzQHOlCHa):

. HZCH2CH Example 27 This example shows the heat-stabilizing efiect onpolyvinyl chloride of the f ollov s iing phosphorus compound:

onaonoion onroonimo omonoionm The following formulation was prepared andtested:

' 0 Parts by weight Dioctyl phthalate 50 Above phosphorus compountL,0.42 Barium cadmium laurate e 2 After milling for 3 minutes at 100pounds gauge presthe' milled mixture was presspolished in a 6 x 6" x0.0625 mold and molded at 170 C. for a period of time equal to'thelength of time required for the platens to reach that temperature (170C.) and at a hydraulic gauge pressure ofca. 1000 psi.

When the molded piece had been'allowed to cool to room temperature itwas cut into 1" x 6" strips, and the latter were placed in a circulatingair oven which was maintained at C. Over a 2.5 'hour period test sampleswere cut from the specimens every 15 minutes in order to determine colorchange if any; Substantially molded specimens no change in color wasnoted; whereas a decided, increasingly significant color. change wasobserved for prepared 'in. the same way but with Y triphenyl 'phosphiteinstead of. the above phosphorus compound.

; Example 28 This example describes evaluation of the compounds l-3,6-11, 13, 15, 1'7, 19,i25, 28,'29, 32,' 33 and' 35 of Example 1 as.plasticizers for cellulose acetate.

Testing iwasconducted .asfollows: Each of said compounds Wasrespectively added at room temperature to a 12% acetone solutionof'cellulos'e acetate, the quantity of said compound being equal byweight to the'quantity of the cellulose acetate in the solution. FilmsWerecast from the resulting mixtures, and the solvent .was allowed toevaporate. .At the endbf about 24 11 11 the films thus Example 29 Theuse of compounds 2, 8, 16, 21-24, 26, 27, 31 and 34 of Example 1 asadjuvants for ethyl cellulose was demonstrated as follows.

To a 5% ethylene dichloride solution of ethyl cellulose (known to thetrade as Ethocell) there was added, respectively, each of said compoundsin a quantity which was equal by weight to that of the ethyl cellulose.Films cast from the resulting mixtures were dried by allowing them tostand at room temperature for about 24 hours. At the end of that timethey were found to be flexible, colorless and transparent and thesurface thereof was free of exudation. No haziness was noted in testsmade with the Photovolt reflection meter.

Example 30 Nitrocellulose was incorporated with each of the compounds1-3, 6-9, 11, 19, 24, 26, 27, 30, 34, and 35 of Example 1.

The following procedure was employed: To a 15% solution ofnitrocellulose in a mixture of toluene and ethanol there was added oneof the above compounds in a quantity equal by weight to that ofnitrocellulose present in the solution. Films cast from the resultingmixtures were air-dried for about 24 hours prior to evaluation. Theywere found to be flexible, colorless and transparent. Testing on thePhotovolt reflection meter disclosed no haziness and there was noexudation of phosphorus compound on the film surface.

Example 31 The compounds 1, 2, 49, 16, 18, 20, 21, 25, 30 and 31 ofExample 1 were tested as flame-retarding agents for ethyl cellulose andfor cellulose acetate.

Each of said components was respectively added to 12% solutions ofcellulose acetate in acetone and to 5% solutions of ethyl cellulose inethylene dichloride, said phosphorus compound being added in a quantityequal to that of the cellulose present in the solutions. Films cast fromthe resulting solutions were air dried for evaporation of solvent. Noneof the films ignited when held just outside of the outer surface of thecone of a Bunsen burner flame. When inserted into the flame, combustionoccurred, but it was extinguished spontaneeously upon withdrawal fromthe flame.

In addition to the compounds tested above, the compounds 3, 10, 12, 13,15, 17, 19, 28, 29, 32, 33 and 35 of Example 1, also gave the sameflame-proofing results when tested by the same procedure with ethylcellulose.

Example 32 tested for use as a flame butyrate and for nitro- CH3 0 CHThe following compound was retardant for cellulose acetate cellulose.

drawal of the igniting flame. On the other hand for a film of the samecellulose ester, alone, burning continues at a rapid rate to completeconsumption of the strip after the igniting flame has been withdrawn.

In another experiment, similarly conducted, a film was cast from asolution containing nitrocellulose and the above compound, the quantityof the latter being 20% by weight of the total solids. That the burningrate of the nitrocellulose was significantly retarded by incorporationof the phorphorus compound was shown by the fact that whereas the timerequired for the flame to travel the length of the test strip was foundto be 12.0 seconds, the flame traveled the length of a like-dimensionedstrip of nitrocellulose, alone, in a time of 5.2 seconds.

Example 33 (A) 0 CH cromomi'mon-iodn ClCH2OH2O hm Ldomomm where n has anaverage value of 2, and

O H P (OCHzCHzCDa ll (OHQCHC1CHIO)BPO CHP (O CHzOHClCHs)! HzCHz Therewere prepared chloroform solutions containing either 42% or 27.5% of (A)or 23% of (B). Strips (1.25 x 6") of the rayon were respectively dippedinto the solutions and then dried at C. for 1 hour. The dried stripswere mounted on a wire mesh trough slanted at 45 C. and ignited by theBunsen burner flame. Upon removal of the flame, combustion ceased; i.e.,the treated fabric was self-extinguishing. On the other hand, the samefabric, untreated, continued to burn after withdrawal of the flame untilit was completely consumed.

Example 34 Flameproofing efliciency of the following compounds wastested against cotton cloth and paper:

II (010132015120) 2]? O CH-CP (0 011 011201) 3 ll (CHaCHOlCHiO) 2P 0 CHP(O CHaCHClCHgh H2OH3 A 2 x 12 inch strip of desized Indian Head cottoncloth was padded with a 15% acetone solution of the above compound I anddried at room temperature to constant weight. The weight increase of thetreated cloth was 20.5%. When held in an open flame, the dried, treatedcloth did not support combustion and the length of charring was lessthan 1.0 inch, i.e., well within the limits set forth by the textileflame-proofing test D626-55T of the American Society for TestingMaterials; The-hand of the treated cloth was smooth and non-harsh andits color had been not at all affected by the treatment.

Similar testing of the above compound II also showed very goodflame-proofing efficiency. When held in the open flame, the treatedcloth did not support combustion and gave a char length of only 0.75inch. Also, when a Whatman No. 1 filter paper was submitted to the sametest, there was obtained a non-flammable paper which charred onlylimitedly.

' The use of the above compound III inthe flame-proofing test againstthe cloth gave a char-length of only 0.25 inch. The treatednon-flammable cloth was of excellent hand and color. Treatment of theIndian Head cloth with acetone, alone, resulted in readilyignitablqhighly flam mable material.

Example 35 This example describes flame-proofing of various com- 7bustible, carbonaceous materials of the present diand polyphorphoruscompounds to the solid materials. The following compounds were tested:

a oionionii ooni (oomomoi): OlCHzOHzO H3- o 0 on. I o owmomioon-i on--ioomomom .o omGHzo (1H3 CHgCHzClJI (11 The materials shownbelow weredipped in 3 3% by weight solutions of the above compounds in chloroform,

' air-dried, and then tested for flame-retardancy against the That theabove papers hadbeen rendered self-extinguishing by application of thepresent compounds is evident fromithe fact that when the correspondingunflame to ignition, upon withburning of the papers does treated papersare held in the drawal of the' burner flame, not cease.

Application, by dipping, of the solutions of either of the compounds'topolyvinyl chloride paper resulted in prevention of blackening and fusionofthe paper when The untreated polyheld in the Bunsen burner flame.vinyl chloride paper blackens and'fuses when so held.

Example 36 V Samples of hardwood (6" x 1" x 0.025) were iminersed forone minute into either an 18.3% chloroform solution or an 11.4%chloroform solution of the following compound:

onzoionzi oonihoongcmoi),

onioiorno H; 7 After oven'drying overnight at a temperature of 83 C.,they were held horizontally in the flame of a Bunsen burner to ignition.Combustion ceased, with no afterglowi as soon as the samples werewithdrawn from the flame. Controls .of the untreated wood or of woodwhichhad been similarly treated with chloroform, alone,

7 withdrawn from the burner flame until they were entirely consumed.

continued 'to burn when 7 Example 7 7 This example shows testing ofcompounds 1-8, 13-18, 2 ,25, and melamine-formaldehyde andurea-formaldehyde resins.

The phosphorus compound was respectively added either to a 30%.

7 solution of the melamine, resin or to a 30% solutionof the urea resinin a-volatile organic solvent, the quantity of phosphoruscompound being33% by weight of the final film in the case of either the urea byapplication of some 35 of Examplel as plasticizers for or melamineresins; Films cast from the resulting solu tions were dried at 140 C.for one hour, and evaluated after being maintained at ordinaryatmospheric conditions for about 24 hours. All of the films weresubstantially colorless'and transparent, and none showed exudation ofplasticizer on the film surface. Thorough compatibility was furtherdemonstrated by the fact that testing on Photovolt reflection meterdisclosed no haziness of the film.

In addition, the melamine-formaldehyde and the ureaformaldehyde resins,were found to give similarly good plasticized films when incorporated ina 1:2 phosphorus compoundzresin weight ratio with the'compound 10, 12,16, 27 of Example 1. j

' Also, like testing of melamine-formaldehyde resin with each of thecompounds 20, 23, 24, 30, 31 and 34 of Example 1, in the 1:2 phosphoruscompound;resin weight ratio gave similarly good films. V 7

Also, testing of the urea formaldehyde resin with by Weight of each ofthe compounds 9, 11 and 19 of Example 1 using the testing proceduredescribed above gave filr'ns having similar clarity, homogeneity andstability.

Example 38 p enyl 0 Films were cast from the resulting solution andairdried using a heat lamp. The films after 24 hours were flexible,clear and transparent. Compatibility of the presently employedphosphorus compound with the nylon fire-retardant study was made by thewas evidenced by the fact that no exudation was noted on the filmsurfaces and that no haziness was observed with the Photovolt reflectionmeter.

Example 39 This example shows the flame retarding eifect of thefollowing compounds on an epoxy resin hardened by phthalic anhydride. 7

* I. n t a oiomonrr-oonr oomomom ciomon o and 0 CH5 0 'CH 0 {L A H g 1 HOHQGHOIOHQQ -o H-P-.0-.. H?P(OCHgCHGlCHa)a OIQHgOHGH LAGH CHCIOHs- Lwhere n has an average value of 0.66.

Respective mixtures consisting of parts by weight of an epoxy resin(Araldite 6020) preparedfrom bisphenol (4,4'-isopropylidene-diphenol)and 'epichlorohydrin, 45 parts by weight of phthalic anhydride and aquantity of one of theabove phosphorus compounds equal to -15 by weightof the total weight of the mixture were heated to Cpand stirred at thistemperature until all of the phthalicanhydride had dissolved. 'Theresulting mixtures were then poured into respective molds which had beenheated to about. C. and cured in an oven at C. for about 4"hours. Acontro for except that no additive was used with the epoxy resin and theanhydride. u 1

Test specimens (6" X05 05) were cut from the cured products. Thespecimen was placed in a trough same procedure, a

3? of 40 mesh screen which was mounted on a ring stand at a 30 ange, anda 2 high, blue flame of the Bunsen burner was applied to the low end ofthe specimen and held there for 10 seconds. After removing the burner,the time to self-extinguishment of the specimen flame was noted. At theend of 60 seconds, the control specimen, i.e., that which did notcontain the phosphorus additive, was still burning with a flame, whereascombustion of the specimens which contained either the above compound Ior the above compound 11 ceased within 22 seconds. Accordingl thehardened epoxy resin had been rendered self-extinguishing byincorporation of said compounds.

Example 40 This example describes preparation of fire-retardant, foamedplastic from a polyalkylene glycol and a dnsocyanate.

A prepolymer was formed as follows: 180 g. of polypropylene glycolhaving a molecular weight of 2000 (Polyglycol P-2000) was blended with0.6 g. of water for 30 minutes under dry nitrogen. There was then added32 g. of 2,4-toluylene diisocyanate and the resulting mixture wasbrought to a temperature of 120 C. within 45 minutes and then held atthis temperature for one hour. After cooling to 50 C., an additional 45g. of the diisocyanate was added, and this was followed by introductionof 14 g. of the following compound CH3 0 GlCHzCHAOOH ii -(BH-(OCH2OH2ODZ I Ll CICHJCHZO CH OCHzCHzCl n where n has an average valueof 2.

To the resulting viscous prepolymer the following were added:

G. Silicone oil 0.2 Water 1.4 N-methylmorpholine 0.6 Triethylamine 0.15

Foaming occurred immediately. The foaming mixture was transferred to amold, and heated first at 70 C. for 20 minutes and then at 120 C. for 3hours. Testing of the resulting cured product for flame resistance,showed it to be self-extinguishing.

Example 41 and parts by welght of the following compound:

II (ClCHzCHzO)2P 0 $11? (0 CHzCHzCDa The resulting 2.0 lbs./ cu. ft.foam was self-extinguishing.

The amove reaction is advantageously conducted by employing the mixingapparatus described in the Hoppe et al. US. Reissue Patent No. 24,514.

Example 42 In the preparation of a flame-proofed polyether flexiblefoam, 100 parts by weight of a prepolymer prepared by 38 reacting amixture of 60 parts by weight of a polyalkylene ether glycol obtained bythe condensation of propylene oxide to a molecular weight of about 2000and 40 parts by weight of a polyalkylene ether triol obtained bycondensing glycerin with propylene oxide to a molecular weight of about3000 with 13.8 parts by weight TD (a mixture consisting of 80%2,4-toluylene diisocyanate and 20% 2,6-toluylene diisocyanate), at 115C. until the reaction mixture had a viscosity of 2000 cps. at 73 C. atwhich time 26.5 parts by weight additional TD-SO was added to produce aprepolymer having an NCO content of 10.6% and a final viscosity of 8500cps. at 25 C., was mixed with 3.0 parts by weight N-ethyl morpholine,0.2 part by weight 1-methyl-4-dimethyl aminoethylpiperazine, 1.0 part byweight polydimethyl siloxane having a viscosity of 50 centistokes at 25C., 2.6 parts by weight water and 10 parts by weight of the followingcompound:

CH3 0 CH3 0 P (O CHzCHClCHa)2 Example 43 in the preparation of aflame-proofed polyester flexible foam parts by weight of a polyesterprepared by the condensation of diethylene glycol, trimethylolpropaneand adipic acid to a molecular weight of about 2500 was mixed with 44parts by weight of 2,4-toluylene diisocyanate, 2.5 parts by weightN-ethyl morpholine, 1.0 part by weight of an emulsifier obtained fromthe reaction of diethylamine and oleic acid, 1.5 parts by weight of anemulsifier (Witco 77-86) obtained by blending polyalcohol carboxylicacid esters with sulfonated natural oils, 3.2 parts by weight water and5 parts by weight of the phosphorus compound tested in Example 41. Theresulting 2.0 lbs./ cu. ft. foam was self-extinguishing.

Instead of using the reaction product of diethylamine and oleic acid asemulsifier, there may be employed any of the emulsifiers which aredisclosed in the Hoppe et al. Reissue Patent No. 24,514.

Example 44 In the preparation of a flame-proofed polyester rigid foam100 parts by weight of a polyester mixture obtained from 80 parts byweight of a polyester prepared by condensing hexane triol, phthalicanhydride, maleic anhydride and adipic acid to .a molecular weight ofabout 1300 and 20 parts by weight of a polyester prepared by condensingphthalic and maleic anhydride, adipic acid, 1,3-butylene glycol andhexane triol to a molecular weight of about 1000 was mixed with 78.3parts by weight TD80 (a mixture consisting of 80% 2,4-toluylenediisocyanate and 20% 2,6-toluylene diisocyanate), 0.5 part by weightN-ethyl morpholine, 9.4 parts by weight of an emulsifier composed of 30%water and 70% sulfonated castor oil and 15 parts by weight of thephosphorus compound tested in Example 41. The resulting foam had adensity of 2.0 lbs/cu. ft. and was flame-proofed.

Example 45 39 it) final prepolymer had an NCO content of about 25% andTesting for flame retardancy was conducted as follows: a viscosity ofabout 3000 cps. at 25 C. was mixed With The respective formulations werediluted with 50% 44 pa s by gh s (2-hydroxypr pyl) aqueous isopropanolto give a 20% solids content. Test ethylendiamillfi, 20 Partsby"Wight.tfichlofo-moflofiulopieces (4 x 4") of air filter paper wererespectively h n and -5 P y Weight Of a POIYSHOXBJI.e Y- 5 dipped intothe solution, squeezed between rubber rolls ylene blocked copolymer and20 Parts by Weight of to obtain a resin content of 28.0i2.0%, and curedfor tha Phosphorus compound testedin Example The 10 minutes at 150 C.'All of the cured paper had good Sultmg. foam had a density of lbsjcuand was Water resistance properties, i.e., dripping of cold tap waterflamc'proofed' on the papers showed no impregnation of the treatedExample 46 10 papers by the water. The flame retardant property of theTh s xample Pro d a p ri n f h l win cured'paper was tested by the TAPPIchar test (T461- cqmp 5 dj s l' p ly f l foams: ,M-48), whereby'a stripof the cured paper is held for 1 Tetrabmmobirsphenol 12 seconds abovethe 1.5 inch flame of a Bunsen II. Tri (2,3-dibr y1) phosphate 15 burner(air supply off) and the char length measured. HI. Tris(2-chloroethyl)phosphate By this test a 3 inch char length or less is regarded to IV.The product: a show good flame-resistance of resin-impregnated airfilter 0 O 0 CH 11 l u I 3 n (CH CHClCH2O)zPOGH POCH P(OCH2CHC1CH3)3oomonoions where n has an average value of 0.66. paper. The presentlyprovided cured papers were shown The compounds were respectively addedin 10% con to give a char length of onyl 2%. Similarly treated andcentrations to the mix just before foaming and hardening. cured airfilter paper prepared in absence of the phos- In each case all oi'fthecomponents of the reaction miX- 'phorus compound but with the samephenolic varnish lS ture and the quantities thereof were the same,except for not flame retardant. the variation in the nature of theadditives, i.e., either I, Example 48 II III or IV was used but not anycombination of them.

.2 tt fthfll ho hous Evaluation of he I gid foams thus Produced gave theg examp 16 shows m a oowmgp r a V r 7 .pound a following results.

if a a H" H Cell Percent Density, Burning g pg V CIOHzOHzPOQEiPtOOH OHOI Additive S1ze Shrinkage lb./ft. rate/mm. tinigllish- 7 C1 CH2 OH? O 7H3. 7 e 7 Using the procedure described in Example 34, the fol- 0 10 2.4. n 3 2 3 8 lowing formulations were evaluated as mpregnatin 1o 2 6 z 5agent for air filter paper. 7 45 5 A0 Formula A: V 1 Percent of totalsolids it will be noted from the above that only the foam 7 Phenom: ''77 V Above phosphorus compd 34.5 prepared from IV, 1.e., one of thepresently provided Eh I ammonium hos hate 7 172 adjuvants isself-extinguishing. that the use of IV results g p p 2 d in leastshrinkage, and that the use of IV gives a product a i of'le ast density.V Formula 13: V 7 Similarly good results were obtained with flexiblepoly Phenolic varnishn 48.3 urethane foams. V A-bove phosphorus compd34.5 V 7 7 Example 47 1 Ethyl ammonium phosphate 17.2 This example showsevaluation of the following 'comhexamethyleneteuamme' pounds with aphenolic varnish in air filter paper ap- 50 The varnish consisted of abase-catalyzed phenol- 7 solids content of 65.0i2.0%.

V plication: 7 .formaldehyde resin in aqueous denatured alcohol and hadBronx 6) in) (IE I (H) 7 V i I Grenada-roan. l oon moongonnionzomo1on=onnromo CH LOOHzOHBlCHH laJn where n, has'anaverage value of 015. 1V i a solids content of 65% i2.0%. Using the testing pro- 7 O p -I Ocedure. described in Example 34, air filter paper prepared 7 H II a withFormula A had a TAPPI char length of 2.75 inches GH3CHC1OHOPOOH2[ PHOOHQCECICHSM and that prepared with Formula B had a char length of GHQHOlCHz-O 7 00112011010133 n I 3.0 inches. The impregnated papers thusobtained had Where n has an average value of 0.66, and V goodflexibility, i.e., the cured papers could be bent and O pleated withoutcracking or tearing the paper. This e 7 showed good plasticizing effectof the phosphorus com- (01120101120) F (O CHZCHfGDI pound on thephenolic resin. All of the cured paper had 0C1; good water resistanceproperties,"i.e., dripping of cold The kn formulations were used; 7 tapWater on the papers showed no impregnation'of the V V V P J treatedpapers by the Water. Determination of the stiffness h b d W HW Solids ofthe cured papers 'on the'Gurley stiffness tester gave a 9 e a 9 Comp 3value of 3650 for the cured papers obtained with Formula g l 1c d5'5"35F-"7TT'Tf T A and a value of 3350Afor that obtainedwith Formula B.

V y m ml P. a -5 Gurley stifiness'loss, determined by substracting theaver- The varnish consisted of a base-catalyzed phenol formg of h 1 and2 t ol from the ag f the, first and second revolution and dividing theresulting aldehyde resin in aqueous, denatured alcohol and had a idifierence by the original value gave a value of 14.5%

1. A COMPOSITION COMPRISING AN ORGANIC POLMER IN CONTACT WITH NOT MORETHAN AN EQUAL AMOUNT, BASED ON THE WEIGHT OF THE POLYMER, OF AN ADJUVANTWHICH IS AN ORGANIC COMPOUND OF THE FORMULA WHERE N IS A NUMBER OF 0 TO2, M IS A NUMBER OF 0 TO 100 WHEN N IS 2 AND 0 WHEN N IS LESS THAN 2, YIS SELECTED FROM THE CLASS CONSISTING OF =P-, $P=O AND $P=S, EACH R ISSELECTED FROM THE CLASS CONSISTING OF HYDROCARBYL, HALOHYDROCARBYL,ALKOXYHYDROCARBYL, AND (HYDROCARBYLOXY)-HALOHYDROCARBYL RADICALS OF FROM1 TO 12 CARBON ATOMS AND SUCH RADICALS LINKED TO THE PHOSPHORUS ATOM OFY BY AN ELEMENT SELECTED FROM THE CLASS CONSISTING OF -O- AND -S- ANDWHEREIN TWO R''S TAKEN TOGETHER STAND FOR A RADICAL SELECTED FROM THECLASS -O-HYDROCARBYLENE-O- AND -O-HALOHYDROCARBYLENE-O- RADICLAS WHICHARE FREE OF ALIPHATIC UNSATURATION AND WHICH CONTAIN FROM 2 TO 10 CARBONATOMS; R'''''' IS SELECTED FROM THE CLASS CONSISTING OF HYDROCARBYL,HALOHYDROCARBYL, ALKOXYHALOHYDROCARBYL AND HYDROCARBYLOXYHALOHYDROCARBYLRADICALS OF FROM 1 TO 12 CARBON ATOMS AND SUCH RADICALS LINKED TO THEPHOSPHORUS ATOMS BY AN ELEMENT SELECTED FROM THE CLASS CONSISTING OF -O-AND -S-; Z IS SELECTED FROM THE CLASS CONSISTING OF HYDROGEN,HYDROCARBYL, HALOHYDROCARBYL, CARBOALKOXYHYDROCARBYL,ALKYLTHIOHYDROCARBYL, ALKXOYHYDROCARBYL, AND CYANOHYDROCARBYL RADICALSOF FROM 1 TO 17 CARBON ATOMS WHEN N IS 2 AND FROM 1 TO 10 CARBON ATOMSWHEN IS LESS THAN 2, AND THE FURYL AND THIENYL RADICALS; AND R'' AND R"ARE SELECTED FROM THE CLASS CONSISTING OF ALKYL, HALOALKYL, ARYL,HALOARYL, ALKOXY, HALOALKOXY, AND (HYDROCARBYLOXY)HALOALKOXY RADICALS OFFROM 1 TO 12 CARBON ATOMS.